CN113856725A - g-C3N4/Fe/MoS2Ternary flower-like heterojunction material and preparation method and application thereof - Google Patents
g-C3N4/Fe/MoS2Ternary flower-like heterojunction material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 71
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 67
- 239000000243 solution Substances 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000005580 one pot reaction Methods 0.000 claims abstract description 3
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- 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 claims description 64
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- 230000000593 degrading effect Effects 0.000 claims description 12
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- 239000002244 precipitate Substances 0.000 claims description 10
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical group [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
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- 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 9
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- 238000002156 mixing Methods 0.000 claims description 6
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- 108010038629 Molybdoferredoxin Proteins 0.000 claims description 2
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 11
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 11
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- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
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- 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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- 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
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to the field of multifunctional materials, and relates to g-C3N4/Fe/MoS2A ternary flower-like heterojunction material, a preparation method and application thereof. Drying the mixed solution of dicyandiamide and ferric nitrate, calcining the dried mixed solution in one pot to obtain g-C3N4Fe, followed by thioacetamide and molybdenum source, hydrothermalCompounding under the condition to obtain g-C with flower-like morphology3N4/Fe/MoS2The presence of molybdenum sulfide enables a solution system to be changed into an acidic microenvironment system suitable for photo-assisted Fenton reaction, and also enables Fe to exist in the ternary flower-shaped heterojunction catalyst2+To Fe3+Better circulation is obtained, and the activity of the reaction is further improved. Meanwhile, the specific surface area is increased due to the unique petal-shaped structure of the catalyst, so that organic pollutants are more easily contacted with active sites, and the photo-assisted Fenton catalytic activity is greatly improved.
Description
Technical Field
The invention belongs to the field of multifunctional materials, and relates to g-C3N4/Fe/MoS2A ternary flower-like heterojunction material, a preparation method and application thereof.
Background
Industrial wastewater contains various non-biodegradable, highly toxic contaminants. In particular, persistent organic pollutants in industrial wastewater are entering the environment and threaten the health of humans and wildlife. The traditional wastewater treatment method cannot effectively remove persistent organic pollutants. To solve this problem, Advanced Oxidation Processes (AOPs), such as ozonation, fenton reaction, and photocatalysis, can remove these persistent organic contaminants.
As one of AOP, Fenton's reaction can activate hydrogen peroxide (H) by using iron ion2O2) Generating hydroxyl radical (. OH). The OH formed as a non-selective radical can remove most of the organic substances in the solution. However, the traditional homogeneous Fenton reaction suffers from narrow pH adaptability and produces iron mud and H2O2Low utilization rate and the like. In order to overcome the disadvantages of the homogeneous Fenton reaction, a heterogeneous Fenton reaction using a solid catalyst was developed. But have some difficulties such as low utilization of visible light and photogenerationThe development of photocatalysis is limited by the rapid recombination of carriers. Nowadays, a synergistic photo-Fenton system combining Fenton and photocatalysis has been proposed to meet the actual demand of treating wastewater which is difficult to treat. The photo-Fenton coupling system is characterized by multiphase Fenton-like reaction and photocatalysis, wherein transition metal (such as Fe)2+/Fe3+) At the sites of the photo-fenton complex prepared by coupling a transition metal to a photocatalyst.
In recent years, g-C3N4As a metal-free photocatalyst, the photocatalyst is widely applied to photocatalytic hydrogen evolution, carbon dioxide reduction and N reduction due to simple synthesis, low cost and excellent photocatalytic performance2Fixation and the like. However, bulk g-C synthesized by direct thermal cracking3N4It is also difficult to form a satisfactory fenton catalyst by compounding with metallic iron because of its unsatisfactory catalytic activity and limited performance due to its low surface area and low efficiency of visible light utilization.
Disclosure of Invention
Aiming at the requirement of the current environment-friendly material, the invention provides g-C3N4/Fe/MoS2The ternary flower-like heterojunction material and the preparation method and application thereof have the advantages of simple production process, strong adaptability and convenient recycling. Metallic iron element in a monoatomic state with g-C3N4The compound is formed into a stably dispersed monoatomic Fe-N4 structure, which not only fully exposes the active sites of Fe, but also promotes the Fe3+/Fe2+Redox cycling activity. And MoS2The nanoparticles are further compounded to construct g-C3N4/Fe/MoS2The ternary system enables an 'acidic microenvironment' to be formed in the Fenton reaction, and the activity of the reaction is further improved. At the same time, the unique petal-shaped structure of the catalyst improves the specific surface area, so that organic pollutants are more easily contacted with active sites. The invention meets the requirement of industrial production and has larger industrial application potential in semiconductor photocatalytic degradation materials.
In order to realize the purpose of the invention, the adopted technical scheme is as follows:
g-C3N4/Fe/MoS2The preparation method of the ternary flower-like heterojunction material comprises the following steps: drying the evenly mixed solution of dicyandiamide and ferric nitrate, calcining the dried evenly mixed solution in a nitrogen atmosphere in one pot to form monoatomic dispersed iron-nitrogen ligand g-C3N4Fe, post-compounding MoS under hydrothermal conditions2At the same time, the catalyst has a flower-like structure, forming the catalytically active compound g-C3N4/Fe/MoS2The ternary flower-shaped heterojunction material greatly improves the comprehensive capabilities of photocatalysis and the like.
The method comprises the following specific steps:
(1) uniformly mixing solution of dicyandiamide and ferric nitrate, drying, heating in nitrogen protection, naturally cooling after heating to obtain solid product in the shape of khaki, grinding to fine powder to obtain g-C3N4/Fe。
(2) Weighing a set amount of g-C prepared in the step (1)3N4Putting Fe in a beaker, adding distilled water, and a set amount of thioacetamide and a molybdenum source (the molybdenum source is sodium molybdate dihydrate and/or sodium molybdate), stirring uniformly (stirring for 30min generally), transferring the mixture into a polytetrafluoroethylene reaction kettle after stirring is finished, heating for reaction, collecting black precipitate, drying, adding a set amount of distilled water after water is completely evaporated, adjusting the pH (to 6.5 generally) with a dilute hydrochloric acid solution, and drying (drying at 60 ℃ generally) to obtain the g-C3N4/Fe/MoS2A ternary flower-like heterojunction material;
g to C described in step (2)3N4The molybdenum-iron atomic ratio of Fe to molybdenum source is 0.75-3.75.
Further, the temperature for preparing the mixed solution in the step (1) is 80 ℃.
Further, the temperature rise rate in the step (1) is 5 ℃/min, the temperature is kept for 4 hours after the heating process of about 2 hours is carried out to reach 550 ℃.
Further, the mass ratio of the ferric nitrate nonahydrate to the dicyandiamide in the step (1) is 0.15.
Further, in the step (2), the reaction temperature is preferably 200 ℃, and the reaction time is preferably 20 h.
Further, the drying conditions in the step (2) are as follows: drying at 60 deg.C for 12 h.
In the above preparation method, g-C3N4Fe and molybdenum disulfide raw materials are fully mixed in a hydrothermal kettle.
g-C obtained by the above method3N4/Fe/MoS2The ternary flower-like heterojunction material is used for efficiently degrading organic pollutants in cooperation with light-assisted Fenton reaction.
The specific application method is as follows: adding the g-C to a solution containing organic contaminants to be degraded3N4/Fe/MoS2The three-element flower-shaped heterojunction material and hydrogen peroxide are subjected to photocatalytic degradation under the irradiation of simulated sunlight (generally 300W visible light xenon lamp irradiation light).
Furthermore, the mass ratio of the hydrogen peroxide to the organic pollutants to be degraded is 1: 3-1: 1.
Further, g-C3N4/Fe/MoS2The mass ratio of the dosage of the ternary flower-shaped heterojunction material to the organic pollutants to be degraded is 10: 1-5: 1.
Further, the organic pollutants are any one or more of rhodamine B, phenol and bisphenol A.
The invention introduces the metallic iron element into g-C in the form of single atom by a molecular assembly mode3N4Is a novel method at present, and forms stable Fe-N4The macrocyclic ligand can improve the adaptability of Fe element to pH value in Fenton reaction, and meanwhile, the stable iron-nitrogen ligand can enhance Fe3+/Fe2+And (4) carrying out oxidation-reduction circulation.
In addition, in order to further improve the photocatalytic activity, a two-dimensional layered nano material MoS is introduced2,MoS2Has an adjustable band gap structure, and the direct (indirect) band gap of the adjustable band gap structure is 1.90eV (1.20 eV). Using molybdenum disulfide to assist in catalyzing a photo-Fenton system through g-C3N4The chemical bonding of the/Fe and the layered molybdenum disulfide successfully constructs a stable three-way hybrid catalyst due to the g-C3N4And molybdenum disulfide are both two-dimensional layered structures, so that a 'composite interlayer region' is constructed in the photo-assisted Fenton reactionThe intermediate region will create a more slightly acidic environment. On one hand, the method is beneficial to the diffusion of organic pollutants in the catalyst, and on the other hand, the Fenton reaction catalyst is promoted to be more active. Fe-N4The existence of macrocyclic ligand and 'composite interlayer region' not only ensure Fe3+/Fe2+Stable circulation on the catalyst surface and exposure to decomposition H2O2And generation of O2More active sites, and weak acidic 'composite interlayer region' can effectively inhibit the generation of iron sludge and protect Fe-N simultaneously4Stability of the macrocyclic ligand.
Compared with the prior art, the invention has the following remarkable advantages: (1) g-C obtained by the process of the invention3N4/Fe/MoS2The nano material has a loose structure with overlapped flower shape and stable Fe-N4The macrocyclic ligand and the weakly acidic composite interlayer region promote the improvement of the photo-assisted Fenton reaction efficiency; (2) the usage amount of the hydrogen peroxide solution is very small and is about 5-10% of that of the traditional Fenton system, and the efficiency of the whole photo-assisted Fenton system is greatly improved; (3) the preparation method is simple, the conditions in the whole preparation process are mild and easy to control, and the method is an effective method capable of improving the degradation efficiency of the carbon nitride composite material; (4) the synthetic raw materials of the invention have low cost, no secondary pollution, reusability and good stability.
Drawings
FIG. 1 shows g-C prepared in example 1 of the present invention3N4/Fe/MoS2The preparation of the ternary flower-like heterojunction material is shown schematically.
FIG. 2 shows g-C prepared in example 1 of the present invention3N4/Fe/MoS2SEM schematic diagram of ternary flower-like heterojunction material.
FIG. 3 shows g-C prepared in example 1 of the present invention3N4/Fe/MoS2XRD schematic diagram of ternary flower-like heterojunction material.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is described in more detail below with reference to the following examples:
example 1
(1) 2g of dicyandiamide and 0.3g of ferric nitrate nonahydrate are weighed into a 100mL beaker and heated to 80 ℃ in a water bath until the components are fully mixed, and then dried for 12 hours at 80 ℃. The dried precursor was then transferred to a crucible with a lid and placed in a tube furnace and heated under nitrogen protection at a rate of 5 ℃/min. After about 2h of heating process, 550 ℃ is reached, and the temperature is kept constant for 4 h. Grinding the solid product obtained by natural cooling to fine powder, and naming the obtained graphite-phase carbon nitride doped with iron as g-C3N4/Fe。
(2) Weighing 1g of g-C prepared in step (1)3N4Fe was placed in a 100ml beaker, and 90mg of sodium molybdate dihydrate and 180mg of thioacetamide were added, and 40ml of distilled water was added, and stirred and mixed at normal temperature for 30 min. Transferring the mixed solution to a reaction kettle with a 100ml polytetrafluoroethylene lining after stirring, carrying out hydrothermal treatment at 200 ℃ for 20h, separating out black precipitate, drying at 60 ℃ for 12h, adding 20ml of distilled water after drying, adding 2mol/L diluted hydrochloric acid solution to adjust the pH value to 6.5, and carrying out secondary drying at the same temperature to obtain g-C3N4/Fe/MoS2A ternary flower-like heterojunction material.
For g-C3N4/Fe/MoS2The method for detecting rhodamine B through photocatalytic degradation of the three-element flower-like heterojunction material comprises the following steps:
photocatalytic degradation of rhodamine B: mixing the above g-C3N4/Fe/MoS2Weighing 10mg of the three-element flower-shaped heterojunction material, and adding 100 mu L of 30% H2O2And putting the solution into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4/Fe/MoS2The visible light degradation rate of rhodamine B in 5 minutes is 95.80%, and the visible light degradation rate of rhodamine B in 10 minutes is 98.12%.
Example 2
(1) 2g of dicyandiamide and 0.3g of ferric nitrate nonahydrate are weighed into a 100mL beaker and heated to 80 ℃ in a water bath until the components are fully mixed, and then dried for 12 hours at 80 ℃. The dried precursor was then transferred to a crucible with a lid and placed in a tube furnace and heated under nitrogen protection at a rate of 5 ℃/min. After about 2h of heating process, 550 ℃ is reached, and the temperature is kept constant for 4 h. Grinding the solid product obtained by natural cooling to fine powder, and naming the obtained graphite-phase carbon nitride doped with iron as g-C3N4/Fe。
(2) Weighing 1g of g-C prepared in step (1)3N4Fe was placed in a 100ml beaker, followed by addition of 135mg of sodium molybdate dihydrate and 270mg of thioacetamide, and addition of 40ml of distilled water, and stirring and mixing at room temperature for 30 min. Transferring the mixed solution into a reaction kettle with a 100ml polytetrafluoroethylene lining after stirring, carrying out hydrothermal treatment at 200 ℃ for 20h, separating out black precipitate, drying at 60 ℃ for 12h, adding 20ml of distilled water after drying, adding 2mol/L diluted hydrochloric acid solution to adjust the pH value to 6.5, carrying out secondary drying at the same temperature, and naming the obtained product as g-C3N4/Fe/MoS2。
For g-C3N4/Fe/MoS2Carrying out photocatalytic degradation rhodamine B detection, wherein the specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2And putting the solution into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4/Fe/MoS2The visible light degradation rate of rhodamine B in 5 minutes is 81.43%, and the visible light degradation rate of rhodamine B in 10 minutes is 93.89%.
Example 3
(1) 2g of dicyandiamide and 0.3g of ferric nitrate nonahydrate are weighed into a 100mL beaker and heated to 80 ℃ in a water bath until the components are fully mixed, and then dried for 12 hours at 80 ℃. The dried precursor was then transferred to a crucible with a lid and placed in a tube furnace and heated under nitrogen protection at a rate of 5 ℃/min. After about 2h of heating process, 550 ℃ is reached, and the temperature is kept constant for 4 h. Grinding the solid product obtained by natural cooling to fine powder, and naming the obtained graphite-phase carbon nitride doped with iron as g-C3N4/Fe。
(2) Weighing 1g of g-C prepared in step (1)3N4Fe was placed in a 100ml beaker, and 180mg of sodium molybdate dihydrate and 360mg of thioacetamide were added, and 40ml of distilled water was added, and stirred and mixed at normal temperature for 30 min. Transferring the mixed solution into a reaction kettle with a 100ml polytetrafluoroethylene lining after stirring, carrying out hydrothermal treatment at 200 ℃ for 20h, separating out black precipitate, drying at 60 ℃ for 12h, adding 20ml of distilled water after drying, adding 2mol/L diluted hydrochloric acid solution to adjust the pH value to 6.5, carrying out secondary drying at the same temperature, and naming the obtained product as g-C3N4/Fe/MoS2。
For g-C3N4/Fe/MoS2Carrying out photocatalytic degradation rhodamine B detection, wherein the specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2And putting the solution into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4/Fe/MoS2The visible light degradation rate of rhodamine B in 4 minutes is 72.63%, and the visible light degradation rate of rhodamine B in 10 minutes is 88.06%.
Example 4
(1) 2g of dicyandiamide and 0.3g of ferric nitrate nonahydrate are weighed into a 100mL beaker and heated to 80 ℃ in a water bath until the components are fully mixed, and then dried for 12 hours at 80 ℃. The dried precursor was then transferred to a crucible with a lid and placed in a tube furnace, heated under nitrogen blanket, and allowed to riseThe temperature rate was 5 ℃/min. After about 2h of heating process, 550 ℃ is reached, and the temperature is kept constant for 4 h. Grinding the solid product obtained by natural cooling to fine powder, and naming the obtained graphite-phase carbon nitride doped with iron as g-C3N4/Fe。
(2) Weighing 1g of g-C prepared in step (1)3N4Fe was placed in a 100ml beaker, and 45mg of sodium molybdate dihydrate and 90mg of thioacetamide were added, and 40ml of distilled water was added, and stirred and mixed at normal temperature for 30 min. Transferring the mixed solution into a reaction kettle with a 100ml polytetrafluoroethylene lining after stirring, carrying out hydrothermal treatment at 200 ℃ for 20h, separating out black precipitate, drying at 60 ℃ for 12h, adding 20ml of distilled water after drying, adding 2mol/L diluted hydrochloric acid solution to adjust the pH value to 6.5, carrying out secondary drying at the same temperature, and naming the obtained product as g-C3N4/Fe/MoS2。
For g-C3N4/Fe/MoS2Carrying out photocatalytic degradation rhodamine B detection, wherein the specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2And putting the solution into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4/Fe/MoS2The visible light degradation rate of rhodamine B in 5 minutes is 65.14%, and the visible light degradation rate of rhodamine B in 10 minutes is 79.31%.
Example 5
(1) 2g of dicyandiamide and 0.3g of ferric nitrate nonahydrate are weighed into a 100mL beaker and heated to 80 ℃ in a water bath until the components are fully mixed, and then dried for 12 hours at 80 ℃. The dried precursor was then transferred to a crucible with a lid and placed in a tube furnace and heated under nitrogen protection at a rate of 5 ℃/min. After about 2h of heating process, 550 ℃ is reached, and the temperature is kept constant for 4 h. Grinding the solid product obtained by natural cooling to fine powder, and naming the obtained graphite-phase carbon nitride doped with iron as g-C3N4/Fe。
(2) Weighing 1g of g-C prepared in step (1)3N4Fe was placed in a 100ml beaker, and 90mg of sodium molybdate dihydrate and 180mg of thioacetamide were added, and 40ml of distilled water was added, and stirred and mixed at normal temperature for 30 min. Transferring the mixed solution to a reaction kettle with a 100ml polytetrafluoroethylene lining after stirring, carrying out hydrothermal treatment at 200 ℃ for 20h, separating out black precipitate, drying at 60 ℃ for 12h, adding 20ml of distilled water after drying, adding 2mol/L dilute hydrochloric acid solution to adjust the pH to 6.5, carrying out secondary drying at the same temperature, and obtaining g-C3N4/Fe/MoS2A ternary flower-like heterojunction material.
For g-C3N4/Fe/MoS2Carrying out photocatalytic degradation phenol detection, wherein the specific detection method comprises the following steps:
photocatalytic degradation of phenol: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2The solution was put into 100mL of a 10mg/L phenol solution, and the phenol was catalytically degraded under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4/Fe/MoS2The degradation rate of phenol was 75.86% in 5 minutes and 96.13% in 10 minutes.
Example 6
(1) 2g of dicyandiamide and 0.3g of ferric nitrate nonahydrate are weighed into a 100mL beaker and heated to 80 ℃ in a water bath until the components are fully mixed, and then dried for 12 hours at 80 ℃. The dried precursor was then transferred to a crucible with a lid and placed in a tube furnace and heated under nitrogen protection at a rate of 5 ℃/min. After about 2h of heating process, 550 ℃ is reached, and the temperature is kept constant for 4 h. Grinding the solid product obtained by natural cooling to fine powder, and naming the obtained graphite-phase carbon nitride doped with iron as g-C3N4/Fe。
(2) Weighing 1g of g-C prepared in step (1)3N4Fe was placed in a 100ml beaker, and 90mg of sodium molybdate dihydrate and 180mg of thioacetamide were added, and 40ml of distilled water was added, and stirred and mixed at normal temperature for 30 min. After the stirring was completed, the mixture was transferred to a 100ml Teflon lined reactor in whichPerforming hydrothermal treatment at 200 deg.C for 20 hr, separating black precipitate, drying at 60 deg.C for 12 hr, adding 20ml distilled water, adding 2mol/L dilute hydrochloric acid solution to adjust pH to 6.5, performing secondary drying at the same temperature to obtain product named as g-C3N4/Fe/MoS2。
For g-C3N4/Fe/MoS2Carrying out photocatalytic degradation bisphenol A detection, wherein the specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2The solution was put into 100mL of a 10mg/L bisphenol A solution, and the bisphenol A was catalytically degraded under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4/Fe/MoS2The visible light degradation rate of bisphenol A in 5 minutes was 76.12%, and the degradation rate of bisphenol A in 10 minutes was 92.23%.
Comparative example 1
Comparative example 1 is different from example 1 in that: the procedure of example 1 was repeated except that the procedure of step (1) was repeated except that iron nitrate nonahydrate was not added in step (1), and the obtained graphite-phase carbon nitride was designated as g-C3N4。
For g-C3N4Carrying out photocatalytic degradation rhodamine B detection, wherein the specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2And putting the solution into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4The visible light degradation rate of rhodamine B in 10 minutes is 0.035%, and the visible light degradation rate of rhodamine B in 60 minutes is 9.75%.
Comparative example 2
Comparative example 1 is different from example 1 in that: the procedure of the step (1) alone was exactly the same as that of the step (1) of example 1, and the obtained graphite-phase carbon nitride was named g-C3N4/Fe。
For g-C3N4The Fe is used for carrying out photocatalytic degradation rhodamine B detection, and the specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2And putting the solution into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4The visible light degradation rate of the rhodamine B in 10 minutes is 37.12 percent, and the visible light degradation rate of the rhodamine B in 60 minutes is 95.9 percent.
Comparative example 3
90mg of sodium molybdate dihydrate and 180mg of thioacetamide are weighed, 40ml of distilled water is added, and stirring and mixing are carried out at normal temperature for 30 min. Transferring the mixed solution into a reaction kettle with a 100ml polytetrafluoroethylene lining after stirring, carrying out hydrothermal treatment at 200 ℃ for 20h, separating out black precipitate, drying at 60 ℃ for 12h, adding 20ml of distilled water after drying, adding 2mol/L diluted hydrochloric acid solution to adjust the pH value to 6.5, carrying out secondary drying at the same temperature, and naming the obtained product as pure MoS2。
To MoS2Carrying out photocatalytic degradation rhodamine B detection, wherein the specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2And putting the solution into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the MoS2The visible light degradation rate of rhodamine B in 10 minutes is 0.068%, and the visible light degradation rate of rhodamine B in 60 minutes is 29.59%.
From the test results of comparative example 1, comparative example 2, comparative example 3 and example 1 described above, it can be seen that (1) bulk carbon nitride also contains pure MoS2The ability to photocatalytically reduce dyes by itself is very limited; (2) iron in the iron-doped carbon nitride can be beneficial to Fenton photoreaction degradation and improvementThe stability of the catalyst structure is reduced, the electron hole recombination rate is reduced, the carrier mobility is reduced, but the improvement effect is limited.
Comparative example 4
(1) 2g of dicyandiamide and 0.3g of ferric nitrate nonahydrate are weighed into a 100mL beaker and heated to 80 ℃ in a water bath until the components are fully mixed, and then dried for 12 hours at 80 ℃. The dried precursor was then transferred to a crucible with a lid and placed in a tube furnace and heated under nitrogen protection at a rate of 5 ℃/min. After about 2h of heating process, 550 ℃ is reached, and the temperature is kept constant for 4 h. Grinding the light yellow solid product obtained by natural cooling to fine powder, and naming the obtained iron-doped graphite-phase carbon nitride as g-C3N4/Fe。
(2) 90mg of sodium molybdate dihydrate and 180mg of thioacetamide are weighed, 40ml of distilled water is added, and stirring and mixing are carried out at normal temperature for 30 min. Transferring the mixed solution into a reaction kettle with a 100ml polytetrafluoroethylene lining after stirring, carrying out hydrothermal treatment at 200 ℃ for 20h, separating out black precipitate, drying at 60 ℃ for 12h, adding 20ml of distilled water after drying, adding 2mol/L diluted hydrochloric acid solution to adjust the pH value to 6.5, carrying out secondary drying at the same temperature, and naming the obtained product as pure MoS2。
(3) Weighing 1g of g-C prepared in step (1)3N4Fe with 0.030g pure MoS2Adding 20ml water, placing in 50ml beaker, further performing ultrasonic treatment for 10min to mix, drying at 60 deg.C for 12 hr to obtain physically mixed catalyst, which is named as g-C3N4/Fe-MoS2。
For g-C3N4/Fe-MoS2Carrying out photocatalytic degradation rhodamine B detection, wherein the specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2And putting the solution into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4/Fe-MoS2The visible light degradation rate of rhodamine B in 10 minutes is 0.017 percent,the visible light degradation rate of rhodamine B in 60 minutes is 0.028%.
As is clear from the above-mentioned test results of comparative example 4 and example 1, (1) in g-C3N4Fe and MoS2The degradation of rhodamine B in the physical mixed system is almost negligible. (2) Compared with a physical mixed system, the chemical compounding method is more beneficial to MoS2The growth on the carbon nitride substrate forms a good multilayer loose structure, and active sites are increased, so that the photocatalytic activity is improved.
Comparative example 5
Comparative example 5 differs from example 1 in that: for g-C3N4/Fe/MoS2When the rhodamine B is subjected to photocatalytic degradation, H is not added2O2The specific detection method of the solution is as follows:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, putting the composite material into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
By testing, the g-C3N4/Fe/MoS2The visible light degradation rate of rhodamine B in 10 minutes is 18.05 percent, and the visible light degradation rate of rhodamine B in 60 minutes is 67.98 percent.
Comparative example 6
Comparative example 6 differs from example 1 in that: the system was run under dark reaction conditions. The specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing 10mg of the composite material, and adding 100 mu L of 30% H2O2And adding the solution into 100mL of 10mg/L rhodamine B solution, and catalytically degrading the rhodamine B under the condition of dark reaction to obtain a degradation curve.
By testing, the g-C3N4/Fe/MoS2The visible light degradation rate of rhodamine B in 10 minutes is 50.05%, and the visible light degradation rate of rhodamine B in 60 minutes is 89.05%.
From the test results of comparative example 6 and example 1 above, it can be seen that the photo-assisted Fenton system degradation relies on excitation by hydrogen peroxide and visible light. Original sourceBecause the hydrogen peroxide is used as an important boosting agent of the Fenton system, Fe2+And H2O2The reaction forms hydroxyl radicals and effectively oxidizes rhodamine B. Then photoexcited electrons and O dissolved in the solution2Combine to form root points O2 -. In general, the traditional homogeneous/heterogeneous Fenton systems differ in Fe2+Oxidation to Fe3+Will generate a hydroxyl radical, which is then substituted by another H2O2Molecular induced reduction back to Fe2+. In contrast, the photo-Fenton system can also excite electrons to promote Fe3+To Fe2+Is detected. Thus, H2O2Use of small amounts may also produce fenton's reaction with enhanced sustainability.
In addition, the applicant also carried out the following validation tests:
1. when dicyandiamide is replaced by melamine, the prepared g-C3N4/Fe sample is easy to form ferric oxide, and the ferric oxide is simply loaded on the surface of g-C3N4, so that the monoatomic high-dispersion state which is proposed by the inventor is difficult to achieve.
2. By a one-step hydrothermal method on CoFe2O4Surface-bonded MoS2The acidic microenvironment is formed, but the microenvironment range is much smaller than that of the present application, mainly because of the g-C prepared in this patent3N4/Fe/MoS2The composite interlayer region is formed, the acid microenvironment range is wider, and the diffusion of organic pollutants in the catalyst is facilitated, so that the catalytic activity is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
Claims (10)
1. g-C3N4/Fe/MoS2The preparation method of the ternary flower-like heterojunction material is characterized by comprising the following steps of: the method comprises the following steps: homogenizing dicyandiamide and ferric nitrateAfter the mixed solution is dried, the mixed solution is calcined in a nitrogen atmosphere in one pot to form monoatomic dispersed iron-nitrogen ligand g-C3N4Fe, then carrying out hydrothermal reaction in the presence of thioacetamide and a molybdenum source to obtain g-C3N4/Fe/MoS2A ternary flower-like heterojunction material.
2. g-C according to claim 13N4/Fe/MoS2The preparation method of the ternary flower-like heterojunction material is characterized by comprising the following steps of: the method comprises the following specific steps:
(1) uniformly mixing solution of dicyandiamide and ferric nitrate, drying, heating in nitrogen protection, naturally cooling after heating to obtain solid product in the shape of khaki, grinding to fine powder to obtain g-C3N4/Fe。
(2) Weighing a set amount of g-C prepared in the step (1)3N4Putting Fe in a beaker, adding distilled water, thioacetamide and a molybdenum source in a set amount, stirring uniformly, transferring the mixture into a polytetrafluoroethylene reaction kettle after stirring is finished, heating for reaction, collecting black precipitate, drying, adding distilled water in a set amount after water is completely evaporated, adjusting the pH value with dilute hydrochloric acid solution, and drying to obtain the g-C3N4/Fe/MoS2A ternary flower-like heterojunction material;
g to C described in step (2)3N4The molybdenum-iron atomic ratio of Fe to molybdenum source is 0.75-3.75.
3. g-C according to claim 23N4/Fe/MoS2The preparation method of the ternary flower-like heterojunction material is characterized by comprising the following steps of: the preparation temperature of the mixed solution in the step (1) is 80 ℃;
and/or, in the step (1), the molybdenum source is sodium molybdate dihydrate and/or sodium molybdate;
and/or, the temperature rise rate in the step (1) is 5 ℃/min, the temperature reaches 550 ℃ after the heating process of about 2 hours, and the temperature is kept for 4 hours;
and/or the mass ratio of the ferric nitrate nonahydrate to the dicyandiamide in the step (1) is 0.15.
4. g-C according to claim 23N4/Fe/MoS2The preparation method of the ternary flower-like heterojunction material is characterized by comprising the following steps of: in the step (2), the reaction temperature is 200 ℃, and the reaction time is 20 hours;
and/or the drying conditions in the step (2) are as follows: drying at 60 deg.C for 12 h;
and/or, the pH is adjusted to 6.5 in step (2).
5. The g-C according to any one of claims 1 to 43N4/Fe/MoS2g-C prepared by preparation method of ternary flower-like heterojunction material3N4/Fe/MoS2A ternary flower-like heterojunction material.
6. g-C according to claim 53N4/Fe/MoS2The application of the ternary flower-like heterojunction material is characterized in that: the method is used for degrading organic pollutants in a synergistic photo-assisted Fenton reaction.
7. g-C according to claim 63N4/Fe/MoS2The application of the ternary flower-like heterojunction material is characterized in that: the specific application method is as follows: adding the g-C to a solution containing organic contaminants to be degraded3N4/Fe/MoS2The ternary flower-shaped heterojunction material and hydrogen peroxide are subjected to photocatalytic degradation under the irradiation of simulated sunlight.
8. g-C according to claim 73N4/Fe/MoS2The application of the ternary flower-like heterojunction material is characterized in that: the mass ratio of the hydrogen peroxide to the organic pollutants to be degraded is 1: 3-1: 1.
9. g-C according to claim 73N4/Fe/MoS2The application of the ternary flower-like heterojunction material is characterized in that: g-C3N4/Fe/MoS2The mass ratio of the dosage of the ternary flower-shaped heterojunction material to the organic pollutant to be degraded is10:1~5:1。
10. g-C according to claim 73N4/Fe/MoS2The application of the ternary flower-like heterojunction material is characterized in that: the organic pollutants are any one or more of rhodamine B, phenol and bisphenol A.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115318311A (en) * | 2022-07-06 | 2022-11-11 | 伊犁师范大学 | FeCN @ MoS 2-x Nano composite material, preparation method and application thereof |
CN115709084A (en) * | 2022-10-24 | 2023-02-24 | 河南师范大学 | Preparation method of Fe-Mo heterojunction multi-core micro-nano material based on sexual propagation yeast regulation |
CN116899611A (en) * | 2023-09-12 | 2023-10-20 | 德州新景环境科技有限公司 | Novel low-temperature catalyst for VOCs treatment, preparation process thereof and treatment method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104415786A (en) * | 2013-09-04 | 2015-03-18 | 安徽大学 | Method for quickly preparing quasi-graphite-structure carbon nitride material by adopting microwave heating |
CN107930665A (en) * | 2017-10-27 | 2018-04-20 | 浙江工商大学 | A kind of two dimension MoS2Photochemical catalyst of regulation and control and its preparation method and application |
CN111375370A (en) * | 2020-01-19 | 2020-07-07 | 北京工业大学 | Fe-g-C3N4Preparation method of multifunctional nano composite material |
CN113058601A (en) * | 2021-03-26 | 2021-07-02 | 华东理工大学 | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting |
-
2021
- 2021-10-18 CN CN202111209127.0A patent/CN113856725B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104415786A (en) * | 2013-09-04 | 2015-03-18 | 安徽大学 | Method for quickly preparing quasi-graphite-structure carbon nitride material by adopting microwave heating |
CN107930665A (en) * | 2017-10-27 | 2018-04-20 | 浙江工商大学 | A kind of two dimension MoS2Photochemical catalyst of regulation and control and its preparation method and application |
CN111375370A (en) * | 2020-01-19 | 2020-07-07 | 北京工业大学 | Fe-g-C3N4Preparation method of multifunctional nano composite material |
CN113058601A (en) * | 2021-03-26 | 2021-07-02 | 华东理工大学 | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting |
Non-Patent Citations (3)
Title |
---|
LINA SU ET AL.: ""Regulating Local Electron Density of Iron Single Sites by Introducing Nitrogen Vacancies for Efficient Photo-Fenton Process"", 《ANGEWANDTE INTERNATIONAL EDITION CHEMIE》 * |
YANGQING HE ET AL.: ""Distinctive binary g-C3N4/MoS2 heterojunctions with highly efficient ultrasonic catalytic degradation for levofloxacin and methylene blue"", 《CERAMICS INTERNATIONAL》 * |
田少鹏等: ""构建MoS2/Fe-g-C3N4异质结催化剂以促进其可见光催化产氢性能"", 《精细化工》 * |
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