CN113856725B - g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction material and preparation method and application thereof - Google Patents
g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113856725B CN113856725B CN202111209127.0A CN202111209127A CN113856725B CN 113856725 B CN113856725 B CN 113856725B CN 202111209127 A CN202111209127 A CN 202111209127A CN 113856725 B CN113856725 B CN 113856725B
- Authority
- CN
- China
- Prior art keywords
- mos
- flower
- ternary
- rhodamine
- heterojunction material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 title description 2
- 239000000243 solution Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 34
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 64
- 229940043267 rhodamine b Drugs 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 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 claims description 12
- 239000012265 solid product Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 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
- 238000000227 grinding Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000356 contaminant Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 230000002195 synergetic effect Effects 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 230000002378 acidificating effect Effects 0.000 abstract description 6
- 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 abstract description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000007777 multifunctional material Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 85
- 230000015556 catabolic process Effects 0.000 description 50
- 238000006731 degradation reaction Methods 0.000 description 50
- 239000002131 composite material Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 229910052724 xenon Inorganic materials 0.000 description 12
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 238000010335 hydrothermal treatment Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 238000011895 specific detection Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910002556 Fe–N4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FWZTTZUKDVJDCM-CEJAUHOTSA-M disodium;(2r,3r,4s,5s,6r)-2-[(2s,3s,4s,5r)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol;iron(3+);oxygen(2-);hydroxide;trihydrate Chemical compound O.O.O.[OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 FWZTTZUKDVJDCM-CEJAUHOTSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- MAJZZCVHPGUSPM-UHFFFAOYSA-N nitric acid nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.O[N+]([O-])=O MAJZZCVHPGUSPM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of multifunctional materials, and relates to g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction material, and preparation method and application thereof. Drying the mixed solution of dicyandiamide and ferric nitrate, and calcining in one pot to obtain g-C 3 N 4 Fe, then compounding with thioacetamide and molybdenum source under hydrothermal condition to obtain g-C with flower-like morphology 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction catalyst, the existence of molybdenum sulfide changes a solution system into an 'acidic micro-environment' system suitable for photo-assisted Fenton reaction, and also enables Fe to be contained in the solution system 2+ To Fe 3+ Better circulation is obtained, and the activity of the reaction is further improved. Meanwhile, the unique petal-shaped structure of the catalyst improves the specific surface area, so that organic pollutants are easier to contact with active sites, and the photo-assisted Fenton catalytic activity of the catalyst is greatly improved.
Description
Technical Field
The invention belongs to the field of multifunctional materials, and relates to g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction material, and preparation method and application thereof.
Background
Industrial wastewater contains a variety of non-biodegradable, highly toxic contaminants. In particular, the entry of persistent organic pollutants in industrial wastewater into the environment poses a health threat to humans and wild animals. The conventional wastewater treatment method cannot effectively remove persistent organic pollutants. To address this problem, advanced Oxidation Processes (AOP) such as ozonation, fenton reaction, photocatalysis, etc., can remove these persistent organic contaminants.
As one of AOPs, the Fenton reaction can be activated by using iron ions to activate hydrogen peroxide (H 2 O 2 ) Hydroxyl radicals (. OH) are generated. As non-selective free radicals, the generated OH can remove most of organic matters in the solution. However, the conventional homogeneous Fenton reaction suffers from narrow pH adaptability, iron sludge generation and H generation 2 O 2 The problem of low utilization rate and the like. In order to overcome the shortcomings of the homogeneous Fenton reaction, heterogeneous Fenton reactions using solid catalysts have been developed. However, problems such as low utilization of visible light and rapid recombination of photogenerated carriers limit the development of photocatalysis. The combination of Fenton and photocatalysis to form a synergistic photo Fenton system has been proposed to meet the actual demands of treating difficult-to-treat wastewater. The photo-Fenton coupling system is characterized by heterogeneous Fenton-like reactions and photocatalysis, in which transition metals (e.g., fe 2+ /Fe 3+ ) Occurs at the site of the photo-Fenton complex prepared by coupling the transition metal to the photocatalyst.
In recent years, g-C 3 N 4 As a metal-free photocatalyst, the catalyst has simple synthesis, low cost and excellent photocatalytic performance and is widely applied to photocatalytic hydrogen evolution, carbon dioxide reduction and N 2 Fixing, etc. However, bulk g-C synthesized by direct thermal cracking 3 N 4 It is also difficult to combine with metallic iron to form a satisfactory Fenton catalyst because of its low surface area and low visible light utilization efficiency with unsatisfactory catalytic activity and limited performance.
Disclosure of Invention
Aiming at the requirements of the current environment-friendly materials, the invention provides a g-C 3 N 4 /Fe/MoS 2 The ternary flower-shaped heterojunction material and the preparation method and application thereof have the advantages of simple production process, strong adaptability and convenient recycling. The metallic iron element is in a monoatomic state and g-C 3 N 4 Compounding to form stable dispersed monoatomic Fe-N4 structure, so as to expose the active site of Fe and promote Fe 3+ /Fe 2+ Redox cycling activity. And MoS 2 The nano particles are further compounded to construct g-C 3 N 4 /Fe/MoS 2 The 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 easier to contact with active sites. The invention meets the requirement of industrial production and has great industrial application potential in the semiconductor photocatalytic degradation material.
In order to achieve the purpose of the invention, the technical scheme adopted is as follows:
g-C 3 N 4 /Fe/MoS 2 The preparation method of the ternary flower-shaped heterojunction material comprises the following steps: drying the uniformly mixed solution of dicyandiamide and ferric nitrate, and calcining in a pot in a nitrogen atmosphere to form the monoatomically dispersed iron-nitrogen ligand g-C 3 N 4 Fe, and then compounding MoS under hydrothermal condition 2 At the same time, the catalyst has a flower-like structure to form a catalytically active compound g-C 3 N 4 /Fe/MoS 2 The ternary flower-shaped heterojunction material can greatly improve comprehensive capacities of photocatalysis and the like.
The method comprises the following specific steps:
(1) Drying the uniformly mixed solution of dicyandiamide and ferric nitrate, heating in nitrogen protection, naturally cooling after heating to obtain a earthy yellow solid product, and grinding the earthy yellow solid product into fine powder to obtain g-C 3 N 4 /Fe。
(2) Weighing a set amount of g-C prepared in the step (1) 3 N 4 Placing Fe in beaker, adding distilled water, adding thioacetamide and molybdenum source (sodium molybdate dihydrate and/or sodium molybdate) in predetermined amounts, stirring to uniformity (generally stirring for 30 min), and transferring to polymer after stirringHeating in tetrafluoroethylene reactor, collecting black precipitate, drying, evaporating water completely, adding distilled water, adjusting pH to 6.5 with dilute hydrochloric acid solution, and drying at 60deg.C to obtain g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction materials;
g-C as described in step (2) 3 N 4 The atomic ratio of Fe to molybdenum source is 0.75-3.75.
Further, the temperature of the mixed solution in the step (1) was 80 ℃.
Further, in the step (1), the temperature rising rate is 5 ℃/min, the temperature reaches 550 ℃ through a heating process of about 2 hours, and the temperature is kept constant for 4 hours.
Further, the mass ratio of ferric nitrate nonahydrate to dicyandiamide in the step (1) is 0.15.
Further, the reaction temperature in the step (2) is preferably 200 ℃, and the reaction time is preferably 20 hours.
Further, the drying conditions in the step (2) are as follows: drying at 60℃for 12h.
In the preparation method, g-C 3 N 4 And (3) fully mixing the Fe and molybdenum disulfide raw materials in a hydrothermal kettle.
g-C obtained by the above method 3 N 4 /Fe/MoS 2 The ternary flower-shaped heterojunction material is used for efficiently degrading organic pollutants in the synergistic light-assisted Fenton reaction.
The specific application method is as follows: adding the g-C to a solution containing the organic contaminant to be degraded 3 N 4 /Fe/MoS 2 The ternary 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).
Further, the mass ratio of the hydrogen peroxide to the organic pollutant to be degraded is 1:3-1:1.
Further, g-C 3 N 4 /Fe/MoS 2 The mass ratio of the consumption of the ternary flower-shaped heterojunction material to the organic pollutant to be degraded is 10: 1-5:1.
Further, the organic pollutant is any one or more of rhodamine B, phenol and bisphenol A.
The invention introduces metallic iron element into g-C in the form of single atom by means of molecular assembly 3 N 4 Is a novel method at present, forms stable Fe-N 4 The macrocyclic ligand can improve the adaptability of Fe element to pH value in Fenton reaction, and the stable Fe-N ligand can enhance Fe 3+ /Fe 2+ And (3) a redox cycle.
In addition, in order to further improve the photocatalytic activity, a two-dimensional layered nanomaterial MoS is introduced 2 ，MoS 2 Has an adjustable band gap structure with a direct (indirect) band gap of 1.90eV (1.20 eV). Molybdenum disulfide is used for promoting a photo Fenton system to pass g-C 3 N 4 Chemical bonding of/Fe and layered molybdenum disulfide, a stable ternary hybrid catalyst was successfully constructed due to g-C 3 N 4 And molybdenum disulfide are two-dimensional layered structures, so that a "composite interlayer region" is constructed in the photo-assisted Fenton reaction, and a relatively large slightly acidic environment is formed in the interlayer region. On one hand, the catalyst is helpful for the diffusion of organic pollutants in the catalyst, and on the other hand, the Fenton reaction catalyst is promoted to be more active. Fe-N 4 The presence of macrocyclic ligands and the "complex interlayer region" not only ensures Fe 3+ /Fe 2+ Stable circulation on the catalyst surface and exposure to decomposition H 2 O 2 And generating O 2 The more active sites of the composite interlayer region which is slightly acidic can effectively inhibit the generation of iron sludge and protect Fe-N 4 Stability of macrocyclic ligands.
Compared with the prior art, the invention has the following remarkable advantages: (1) g-C prepared by the method 3 N 4 /Fe/MoS 2 The nano material has a flower-like overlapped loose structure and stable Fe-N 4 The macrocyclic ligand and the weak acidic 'composite interlayer region' promote the improvement of the efficiency of the photo-assisted Fenton reaction; (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 light-assisted Fenton system is greatly improved; (3) The preparation method of the invention is simple and the whole preparation processThe conditions 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 invention has low cost of synthetic raw materials, no secondary pollution, repeated use and good stability.
Drawings
FIG. 1 shows the g-C of example 1 of the present invention 3 N 4 /Fe/MoS 2 Schematic preparation of ternary flower-like heterojunction materials.
FIG. 2 shows the g-C of example 1 of the present invention 3 N 4 /Fe/MoS 2 SEM schematic of ternary flower-like heterojunction material.
FIG. 3 shows the g-C of example 1 of the present invention 3 N 4 /Fe/MoS 2 XRD schematic 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 various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
example 1
(1) 2g dicyandiamide and 0.3g ferric nitrate nonahydrate are weighed into a 100mL beaker and heated in a water bath to 80 ℃ to be fully mixed, and then dried for 12 hours under the condition of 80 ℃. The dried precursor was then transferred to a covered crucible and placed in a tube furnace and heated under nitrogen at a rate of 5 ℃/min. The temperature reached 550℃over a heating period of about 2 hours and was kept constant for 4 hours. Grinding the naturally cooled earthy yellow solid product to fine powder, and naming the obtained iron-doped graphite phase carbon nitride as g-C 3 N 4 /Fe。
(2) Weighing 1g of g-C prepared in the step (1) 3 N 4 In a 100ml beaker, add 90mg of sodium molybdate dihydrate and 180mg of thioacetamide, and40ml of distilled water was added thereto and stirred and mixed at room temperature for 30 minutes. Transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining of 100ml after stirring, performing hydrothermal treatment at 200 ℃ for 20 hours, separating black precipitate, drying at 60 ℃ for 12 hours, adding 20ml of distilled water after drying, adding 2mol/L of dilute hydrochloric acid solution to adjust the pH to 6.5, and performing secondary drying at the same temperature to obtain g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction materials.
For g-C 3 N 4 /Fe/MoS 2 The detection method for carrying out photocatalytic degradation on rhodamine B by using the ternary flower-shaped heterojunction material comprises the following steps:
photocatalytic degradation of rhodamine B: the above g-C 3 N 4 /Fe/MoS 2 10mg of ternary flower-like heterojunction material is weighed and 100 mu L of 30% H is added 2 O 2 And (3) adding 100mL of 10mg/L rhodamine B solution into the solution, and carrying out catalytic degradation on rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the g-C 3 N 4 /Fe/MoS 2 The visible light degradation rate of rhodamine B is 95.80% within 5 minutes, and the visible light degradation rate of rhodamine B is 98.12% within 10 minutes.
Example 2
(1) 2g dicyandiamide and 0.3g ferric nitrate nonahydrate are weighed into a 100mL beaker and heated in a water bath to 80 ℃ to be fully mixed, and then dried for 12 hours under the condition of 80 ℃. The dried precursor was then transferred to a covered crucible and placed in a tube furnace and heated under nitrogen at a rate of 5 ℃/min. The temperature reached 550℃over a heating period of about 2 hours and was kept constant for 4 hours. Grinding the naturally cooled earthy yellow solid product to fine powder, and naming the obtained iron-doped graphite phase carbon nitride as g-C 3 N 4 /Fe。
(2) Weighing 1g of g-C prepared in the step (1) 3 N 4 the/Fe was placed in a 100ml beaker, 135mg of sodium molybdate dihydrate and 270mg of thioacetamide were added, and 40ml of distilled water was added, and stirred and mixed at room temperature for 30 minutes. Transferring the mixed solution to a reaction kettle with a polytetrafluoroethylene lining of 100ml after stirring, carrying out hydrothermal treatment for 20h at 200 ℃,separating black precipitate, drying at 60deg.C for 12 hr, adding 20ml distilled water, adding 2mol/L diluted hydrochloric acid solution to adjust pH to 6.5, and drying at the same temperature for the second time to give the final product called g-C 3 N 4 /Fe/MoS 2 。
For g-C 3 N 4 /Fe/MoS 2 The detection method for the photocatalytic degradation of rhodamine B comprises the following steps:
photocatalytic degradation of rhodamine B: weighing the composite material to 10mg, adding 100 mu L of 30% H 2 O 2 And (3) adding 100mL of 10mg/L rhodamine B solution into the solution, and carrying out catalytic degradation on rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the g-C 3 N 4 /Fe/MoS 2 The visible light degradation rate of rhodamine B is 81.43% within 5 minutes, and the visible light degradation rate of rhodamine B is 93.89% within 10 minutes.
Example 3
(1) 2g dicyandiamide and 0.3g ferric nitrate nonahydrate are weighed into a 100mL beaker and heated in a water bath to 80 ℃ to be fully mixed, and then dried for 12 hours under the condition of 80 ℃. The dried precursor was then transferred to a covered crucible and placed in a tube furnace and heated under nitrogen at a rate of 5 ℃/min. The temperature reached 550℃over a heating period of about 2 hours and was kept constant for 4 hours. Grinding the naturally cooled earthy yellow solid product to fine powder, and naming the obtained iron-doped graphite phase carbon nitride as g-C 3 N 4 /Fe。
(2) Weighing 1g of g-C prepared in the step (1) 3 N 4 the/Fe was placed in a 100ml beaker, 180mg of sodium molybdate dihydrate and 360mg of thioacetamide were added, and 40ml of distilled water was added, and stirred and mixed at room temperature for 30 minutes. Transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining of 100ml after stirring, carrying out hydrothermal treatment at 200 ℃ for 20 hours, separating black precipitate, drying at 60 ℃ for 12 hours, adding 20ml of distilled water after drying, adding 2mol/L of dilute hydrochloric acid solution to adjust the pH of the solution to 6.5, and carrying out secondary drying at the same temperature, thereby obtaining a product named g-C 3 N 4 /Fe/MoS 2 。
For g-C 3 N 4 /Fe/MoS 2 The detection method for the photocatalytic degradation of rhodamine B comprises the following steps:
photocatalytic degradation of rhodamine B: weighing the composite material to 10mg, adding 100 mu L of 30% H 2 O 2 And (3) adding 100mL of 10mg/L rhodamine B solution into the solution, and carrying out catalytic degradation on rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the g-C 3 N 4 /Fe/MoS 2 The visible light degradation rate of rhodamine B is 72.63% within 4 minutes, and the visible light degradation rate of rhodamine B is 88.06% within 10 minutes.
Example 4
(1) 2g dicyandiamide and 0.3g ferric nitrate nonahydrate are weighed into a 100mL beaker and heated in a water bath to 80 ℃ to be fully mixed, and then dried for 12 hours under the condition of 80 ℃. The dried precursor was then transferred to a covered crucible and placed in a tube furnace and heated under nitrogen at a rate of 5 ℃/min. The temperature reached 550℃over a heating period of about 2 hours and was kept constant for 4 hours. Grinding the naturally cooled earthy yellow solid product to fine powder, and naming the obtained iron-doped graphite phase carbon nitride as g-C 3 N 4 /Fe。
(2) Weighing 1g of g-C prepared in the step (1) 3 N 4 the/Fe was placed in a 100ml beaker, 45mg of sodium molybdate dihydrate and 90mg of thioacetamide were added, and 40ml of distilled water was added, and stirred and mixed at room temperature for 30 minutes. Transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining of 100ml after stirring, carrying out hydrothermal treatment at 200 ℃ for 20 hours, separating black precipitate, drying at 60 ℃ for 12 hours, adding 20ml of distilled water after drying, adding 2mol/L of dilute hydrochloric acid solution to adjust the pH of the solution to 6.5, and carrying out secondary drying at the same temperature, thereby obtaining a product named g-C 3 N 4 /Fe/MoS 2 。
For g-C 3 N 4 /Fe/MoS 2 The detection method for the photocatalytic degradation of rhodamine B comprises the following steps:
photocatalytic degradation of rhodamine B: weighing the above composite material 10mg, adding100 mu L of 30% H 2 O 2 And (3) adding 100mL of 10mg/L rhodamine B solution into the solution, and carrying out catalytic degradation on rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the g-C 3 N 4 /Fe/MoS 2 The visible light degradation rate of rhodamine B is 65.14% within 5 minutes, and the visible light degradation rate of rhodamine B is 79.31% within 10 minutes.
Example 5
(1) 2g dicyandiamide and 0.3g ferric nitrate nonahydrate are weighed into a 100mL beaker and heated in a water bath to 80 ℃ to be fully mixed, and then dried for 12 hours under the condition of 80 ℃. The dried precursor was then transferred to a covered crucible and placed in a tube furnace and heated under nitrogen at a rate of 5 ℃/min. The temperature reached 550℃over a heating period of about 2 hours and was kept constant for 4 hours. Grinding the naturally cooled earthy yellow solid product to fine powder, and naming the obtained iron-doped graphite phase carbon nitride as g-C 3 N 4 /Fe。
(2) Weighing 1g of g-C prepared in the step (1) 3 N 4 the/Fe was placed in a 100ml beaker, and 90mg of sodium molybdate dihydrate and 180mg of thioacetamide were added thereto, and 40ml of distilled water was added thereto, and mixed by stirring at normal temperature for 30 minutes. Transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining of 100ml after stirring, performing hydrothermal treatment at 200 ℃ for 20 hours, separating black precipitate, drying at 60 ℃ for 12 hours, adding 20ml of distilled water after drying, adding 2mol/L of dilute hydrochloric acid solution to adjust the pH to 6.5, performing secondary drying at the same temperature, and obtaining g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction materials.
For g-C 3 N 4 /Fe/MoS 2 The method for detecting the photocatalytic degradation of phenol comprises the following steps:
photocatalytic degradation of phenol: weighing the composite material to 10mg, adding 100 mu L of 30% H 2 O 2 And (3) adding the solution into 100mL of 10mg/L phenol solution, and carrying out catalytic degradation on phenol under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the g-C 3 N 4 /Fe/MoS 2 The degradation rate of phenol was 75.86% in 5 minutes and 96.13% in 10 minutes.
Example 6
(1) 2g dicyandiamide and 0.3g ferric nitrate nonahydrate are weighed into a 100mL beaker and heated in a water bath to 80 ℃ to be fully mixed, and then dried for 12 hours under the condition of 80 ℃. The dried precursor was then transferred to a covered crucible and placed in a tube furnace and heated under nitrogen at a rate of 5 ℃/min. The temperature reached 550℃over a heating period of about 2 hours and was kept constant for 4 hours. Grinding the naturally cooled earthy yellow solid product to fine powder, and naming the obtained iron-doped graphite phase carbon nitride as g-C 3 N 4 /Fe。
(2) Weighing 1g of g-C prepared in the step (1) 3 N 4 the/Fe was placed in a 100ml beaker, and 90mg of sodium molybdate dihydrate and 180mg of thioacetamide were added thereto, and 40ml of distilled water was added thereto, and mixed by stirring at normal temperature for 30 minutes. Transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining of 100ml after stirring, carrying out hydrothermal treatment at 200 ℃ for 20 hours, separating black precipitate, drying at 60 ℃ for 12 hours, adding 20ml of distilled water after drying, adding 2mol/L of dilute hydrochloric acid solution to adjust the pH of the solution to 6.5, and carrying out secondary drying at the same temperature, thereby obtaining a product named g-C 3 N 4 /Fe/MoS 2 。
For g-C 3 N 4 /Fe/MoS 2 The method for detecting the photocatalytic degradation bisphenol A comprises the following steps:
photocatalytic degradation of rhodamine B: weighing the composite material to 10mg, adding 100 mu L of 30% H 2 O 2 And (3) putting the solution into 100mL of 10mg/L bisphenol A solution, and carrying out catalytic degradation on bisphenol A under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the g-C 3 N 4 /Fe/MoS 2 The visible light degradation rate of bisphenol A was 76.12% in 5 minutes, and the degradation rate of bisphenol A was 92.23% in 10 minutes.
Comparative example 1
Comparative example 1 is different from example 1 in that: only step (1) is carried out and no nitrate nonahydrate is addedIron acid, otherwise the same operation as in step (1) of example 1, the resulting graphite-phase carbon nitride was designated g-C 3 N 4 。
For g-C 3 N 4 The detection method for the photocatalytic degradation of rhodamine B comprises the following steps:
photocatalytic degradation of rhodamine B: weighing the composite material to 10mg, adding 100 mu L of 30% H 2 O 2 And (3) adding 100mL of 10mg/L rhodamine B solution into the solution, and carrying out catalytic degradation on rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the g-C 3 N 4 The visible light degradation rate of rhodamine B is 0.035% within 10 minutes, and the visible light degradation rate of rhodamine B is 9.75% within 60 minutes.
Comparative example 2
Comparative example 1 is different from example 1 in that: the procedure of step (1) alone was exactly the same as that of step (1) of example 1, and the resulting graphite-phase carbon nitride was designated as g-C 3 N 4 /Fe。
For g-C 3 N 4 And (3) detecting the rhodamine B by carrying out photocatalytic degradation on Fe, wherein the specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing the composite material to 10mg, adding 100 mu L of 30% H 2 O 2 And (3) adding 100mL of 10mg/L rhodamine B solution into the solution, and carrying out catalytic degradation on rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the g-C 3 N 4 The visible light degradation rate of rhodamine B is 37.12% in 10 minutes, and the visible light degradation rate of rhodamine B is 95.9% in 60 minutes.
Comparative example 3
90mg of sodium molybdate dihydrate and 180mg of thioacetamide are weighed, 40ml of distilled water is added, and the mixture is stirred and mixed for 30 minutes at normal temperature. After the completion of stirring, the mixture was transferred to a 100ml polytetrafluoroethylene-lined reaction vessel, subjected to hydrothermal treatment at 200℃for 20 hours, the black precipitate was separated and dried at 60℃for 12 hours, and after the completion of drying, 20ml of distilled water was added, and a 2mol/L diluted hydrochloric acid solution was added to adjust the pH to 6.5, drying at the same temperature for the second time, and obtaining the product named as pure MoS 2 。
For MoS 2 The detection method for the photocatalytic degradation of rhodamine B comprises the following steps:
photocatalytic degradation of rhodamine B: weighing the composite material to 10mg, adding 100 mu L of 30% H 2 O 2 And (3) adding 100mL of 10mg/L rhodamine B solution into the solution, and carrying out catalytic degradation on rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the MoS 2 The visible light degradation rate of rhodamine B is 0.068% within 10 minutes, and the visible light degradation rate of rhodamine B is 29.59% within 60 minutes.
From the above test results of comparative example 1, comparative example 2, comparative example 3 and example 1, it can be seen that (1) bulk carbon nitride also has pure MoS 2 The ability to photocatalytically degrade dyes is very limited per se; (2) The iron in the iron-doped carbon nitride can be helpful for Fenton photoreaction degradation, the stability of the catalyst structure is improved, the electron-hole recombination rate is reduced, the carrier mobility is reduced, but the improvement effect is limited.
Comparative example 4
(1) 2g dicyandiamide and 0.3g ferric nitrate nonahydrate are weighed into a 100mL beaker and heated in a water bath to 80 ℃ to be fully mixed, and then dried for 12 hours under the condition of 80 ℃. The dried precursor was then transferred to a covered crucible and placed in a tube furnace and heated under nitrogen at a rate of 5 ℃/min. The temperature reached 550℃over a heating period of about 2 hours and was kept constant for 4 hours. Grinding the pale yellow solid product obtained by natural cooling into fine powder, and naming the obtained iron-doped graphite phase carbon nitride as g-C 3 N 4 /Fe。
(2) 90mg of sodium molybdate dihydrate and 180mg of thioacetamide are weighed, 40ml of distilled water is added, and the mixture is stirred and mixed for 30 minutes at normal temperature. Transferring the mixture to a 100ml polytetrafluoroethylene-lined reaction kettle after stirring, performing hydrothermal treatment at 200deg.C for 20h, separating black precipitate, drying at 60deg.C for 12h, adding 20ml distilled water after drying, adding 2mol/L diluted hydrochloric acid solution to adjust pH to 6.5, and performing the same processIs subjected to a second drying at a temperature of (2) and the product obtained is designated as pure MoS 2 。
(3) Weighing 1g of g-C prepared in the step (1) 3 N 4 Fe and 0.030g pure MoS 2 Adding 20ml of water into a 50ml beaker, carrying out ultrasonic treatment for 10min to mix, drying at 60 ℃ for 12h to obtain a physically mixed catalyst, and naming the physically mixed catalyst as g-C 3 N 4 /Fe-MoS 2 。
For g-C 3 N 4 /Fe-MoS 2 The detection method for the photocatalytic degradation of rhodamine B comprises the following steps:
photocatalytic degradation of rhodamine B: weighing the composite material to 10mg, adding 100 mu L of 30% H 2 O 2 And (3) adding 100mL of 10mg/L rhodamine B solution into the solution, and carrying out catalytic degradation on rhodamine B under the irradiation of a 300W visible light xenon lamp to obtain a degradation curve.
Through the test, the g-C 3 N 4 /Fe-MoS 2 The visible light degradation rate of rhodamine B is 0.017% within 10 minutes, and the visible light degradation rate of rhodamine B is 0.028% within 60 minutes.
As can be seen from the test results of comparative example 4 and example 1 described above, (1) in g-C 3 N 4 Fe and MoS 2 The 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 MoS 2 And the growth on the carbon nitride substrate forms a good multi-layer loose structure, and active sites are increased so as to improve the photocatalytic activity.
Comparative example 5
Comparative example 5 is different from example 1 in that: for g-C 3 N 4 /Fe/MoS 2 H is not added when the detection of the photocatalytic degradation rhodamine B is carried out 2 O 2 The specific detection method of the solution comprises the following steps:
photocatalytic degradation of rhodamine B: 10mg of the composite material is weighed and put into 100mL of 10mg/L rhodamine B solution, and under the irradiation of a 300W visible light xenon lamp, the rhodamine B is catalytically degraded to obtain a degradation curve.
Through the test, the g-C 3 N 4 /Fe/MoS 2 The visible light degradation rate of rhodamine B is 18.05% within 10 minutes, and the visible light degradation rate of rhodamine B is 67.98% within 60 minutes.
Comparative example 6
Comparative example 6 is different from example 1 in that: the system is carried out under dark reaction conditions. The specific detection method comprises the following steps:
photocatalytic degradation of rhodamine B: weighing the composite material to 10mg, adding 100 mu L of 30% H 2 O 2 And (3) adding 100mL of 10mg/L rhodamine B solution into the solution, and carrying out catalytic degradation on the rhodamine B under the condition of dark reaction to obtain a degradation curve.
Through the test, the g-C 3 N 4 /Fe/MoS 2 The visible light degradation rate of rhodamine B is 50.05% within 10 minutes, and the visible light degradation rate of rhodamine B is 89.05% within 60 minutes.
From the test results of comparative example 6 and example 1 described above, it is clear that the degradation of the photo-assisted Fenton system depends on the excitation of hydrogen peroxide and visible light. The reason is that hydrogen peroxide is used as an important booster of the Fenton system, fe 2+ And H is 2 O 2 The reaction forms hydroxyl radicals and effectively oxidizes rhodamine B. Photoexcitation of electrons and dissolution of O in solution 2 Combine to form root point O 2 - . In general, conventional homogeneous/heterogeneous Fenton systems are distinguished by Fe 2+ Oxidation to Fe 3+ Hydroxyl radicals are generated in the course of (2) and then are replaced by another H 2 O 2 Molecular induced reduction of Fe back 2+ . In contrast, the photo Fenton system can also excite electrons to promote Fe 3+ To Fe 2+ Is a transition of (c). Thus H 2 O 2 The use of small amounts may also produce Fenton's reaction with enhanced sustainability.
In addition, the applicant has also performed the following verification tests:
1. when dicyandiamide is replaced by melamine, the prepared metal iron in the g-C3N4/Fe sample easily forms ferric oxide, is simply loaded on the surface of the g-C3N4, and is difficult to achieve the monoatomic high-dispersion state.
2. In a one-step hydrothermal methodCoFe 2 O 4 Surface-bonded MoS 2 An acidic microenvironment is formed, but its microenvironment range is much smaller than the present application, mainly due to the g-C prepared in this patent 3 N 4 /Fe/MoS 2 The region between the composite layers is formed, the acid microenvironment range is larger, and the diffusion of organic pollutants in the catalyst is facilitated, so that the catalytic activity is improved.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
Claims (6)
1. g-C for degrading organic pollutants in synergistic light-assisted Fenton reaction 3 N 4 /Fe/MoS 2 The application of the ternary flower-shaped heterojunction material is characterized in that: the specific application method is as follows: adding g-C to a solution containing an organic contaminant to be degraded 3 N 4 /Fe/MoS 2 The ternary flower-shaped heterojunction material and hydrogen peroxide are subjected to photocatalytic degradation under the irradiation of simulated sunlight;
g-C 3 N 4 /Fe/MoS 2 the preparation method of the ternary flower-shaped heterojunction material comprises the following steps:
(1) The evenly mixed solution of dicyandiamide and ferric nitrate nonahydrate is heated in nitrogen protection after being dried to form the monoatomically dispersed iron-nitrogen ligand g-C 3 N 4 And (3) after heating, naturally cooling to obtain a earthy yellow solid product, grinding the earthy yellow solid product into fine powder to obtain g-C 3 N 4 /Fe；
(2) Weighing a set amount of g-C prepared in the step (1) 3 N 4 Placing Fe in beaker, adding distilled water, adding thioacetamide and molybdenum source, stirring to uniformity, transferring into polytetrafluoroethylene reaction kettle, heating to obtain black precipitate, drying, evaporating water completely, adding distilled water, and regulating with diluted hydrochloric acid solutionpH, and drying to obtain the g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction materials;
g-C as described in step (2) 3 N 4 The atomic ratio of Fe to molybdenum source is 0.75-3.75, the reaction temperature is 200 ℃, the reaction time is 20h, and the pH is adjusted to 6.5.
2. g-C for degrading organic contaminants in a synergistic light-assisted Fenton reaction according to claim 1 3 N 4 /Fe/MoS 2 The application of the ternary flower-shaped heterojunction material is characterized in that: the configuration temperature of the mixed solution in the step (1) is 80 ℃;
and/or, in the step (1), the heating rate is 5 ℃/min, the temperature reaches 550 ℃ through a heating process of 2 hours, and the temperature is kept for 4 hours;
and/or the mass ratio of ferric nitrate nonahydrate to dicyandiamide in the step (1) is 0.15.
3. g-C for degrading organic contaminants in a synergistic light-assisted Fenton reaction according to claim 1 3 N 4 /Fe/MoS 2 The application of the ternary flower-shaped heterojunction material is characterized in that: the drying conditions in the step (2) are as follows: drying at 60 ℃ for 12 hours;
and/or, in the step (2), the molybdenum source is sodium molybdate dihydrate and/or sodium molybdate.
4. g-C for degrading organic contaminants in a synergistic light-assisted Fenton reaction according to claim 1 3 N 4 /Fe/MoS 2 The application of the ternary flower-shaped heterojunction material is characterized in that: the mass ratio of the hydrogen peroxide to the organic pollutant to be degraded is 1:3-1:1.
5. g-C according to claim 1 3 N 4 /Fe/MoS 2 The application of the ternary flower-shaped heterojunction material is characterized in that: g-C 3 N 4 /Fe/MoS 2 The mass ratio of the consumption of the ternary flower-shaped heterojunction material to the organic pollutant to be degraded is 10:1-5:1.
6. g-C for degrading organic contaminants in a synergistic light-assisted Fenton reaction according to claim 1 3 N 4 /Fe/MoS 2 The application of the ternary flower-shaped heterojunction material is characterized in that: the organic pollutant is any one or more of rhodamine B, phenol and bisphenol A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111209127.0A CN113856725B (en) | 2021-10-18 | 2021-10-18 | g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111209127.0A CN113856725B (en) | 2021-10-18 | 2021-10-18 | g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113856725A CN113856725A (en) | 2021-12-31 |
| CN113856725B true CN113856725B (en) | 2023-06-23 |
Family
ID=79000062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111209127.0A Active CN113856725B (en) | 2021-10-18 | 2021-10-18 | g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113856725B (en) |
Families Citing this family (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 |
| CN115709084B (en) * | 2022-10-24 | 2024-02-06 | 河南师范大学 | Preparation method of Fe-Mo heterojunction polynuclear micro-nano material based on sexual propagation yeast regulation and control |
| CN116899611B (en) * | 2023-09-12 | 2023-12-01 | 德州新景环境科技有限公司 | Low-temperature catalyst for VOCs treatment, preparation process thereof and treatment method thereof |
Family Cites Families (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 |
| CN107930665B (en) * | 2017-10-27 | 2019-10-01 | 浙江工商大学 | A kind of two dimension MoS2Photochemical catalyst of regulation 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 |
| CN113058601B (en) * | 2021-03-26 | 2022-09-09 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN113856725A (en) | 2021-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Enhanced visible light photo-Fenton-like degradation of tetracyclines by expanded perlite supported FeMo3Ox/g-C3N4 floating Z-scheme catalyst | |
| CN113856725B (en) | g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction material and preparation method and application thereof | |
| Pang et al. | Rapid Cr (VI) reduction in aqueous solution using a novel microwave-based treatment with MoS2-MnFe2O4 composite | |
| CN106957438B (en) | Preparation of modified MIL-53(Fe) metal organic framework and method for treating organic wastewater by activating persulfate | |
| He et al. | High efficient visible-light photocatalytic performance of Cu/ZnO/rGO nanocomposite for decomposing of aqueous ammonia and treatment of domestic wastewater | |
| CN106391089B (en) | A kind of carbonitride load iron oxide photocatalyst of efficient degradation p-nitrophenol | |
| CN112808313B (en) | Nitrogen-doped carbon quantum dot/metal organic framework material MOF-5 photocatalyst and preparation method and application thereof | |
| Zhao et al. | Faster electron injection and higher interface reactivity in g-C3N4/Fe2O3 nanohybrid for efficient photo-Fenton-like activity toward antibiotics degradation | |
| Feng et al. | Improved photocatalytic conversion of high− concentration ammonia in water by low− cost Cu/TiO2 and its mechanism study | |
| Fan et al. | Degradation of acetaminophen in aqueous solution under visible light irradiation by Bi-modified titanate nanomaterials: morphology effect, kinetics and mechanism | |
| Li et al. | Fe and Cu co-doped graphitic carbon nitride as an eco-friendly photo-assisted catalyst for aniline degradation | |
| CN111821982B (en) | Graphene oxide-cerium oxide-ferric oxide composite material, synthetic method and application thereof in catalytic degradability | |
| WO2019029513A1 (en) | Fenton catalyst, preparation method therefor, and application thereof | |
| Liu et al. | Synergistic effect of single-atom Cu and hierarchical polyhedron-like Ta3N5/CdIn2S4 S-scheme heterojunction for boosting photocatalytic NH3 synthesis | |
| CN113398974A (en) | Fe-doped g-C3N4Photocatalyst and preparation method and application thereof | |
| CN108671951B (en) | Carbon nitride composite photocatalyst and preparation method and application thereof | |
| Ye et al. | Photo-Fenton and oxygen vacancies' synergy for enhancing catalytic activity with S-scheme FeS 2/Bi 2 WO 6 heterostructure | |
| Sun et al. | Efficient peroxymonosulfate activation of immobilized Fe–N–C catalyst on ceramsite for the continuous flow removal of phenol | |
| Luo et al. | CoFe-LDO nanoparticles as a novel catalyst of peroxymonosulfate (PMS) for histidine removal | |
| Ma et al. | Iron pyrophosphate doped carbon nanocomposite for tetracycline degradation by activation of peroxymonosulfate | |
| CN117643900B (en) | Preparation method and application of S-type heterojunction copper ferrite/zinc indium sulfide visible light catalyst | |
| Zhao et al. | ZIF-8-derived hollow carbon polyhedra with highly accessible single Mn-N6 sites as peroxymonosulfate activators for efficient sulfamethoxazole degradation | |
| Wang et al. | Construction of a novel Cu 2 (OH) 3 F/gC 3 N 4 heterojunction as a high-activity Fenton-like catalyst driven by visible light | |
| CN110813358A (en) | Ag2O-ZnO/g-C3N4Preparation method of photocatalytic ozonization catalyst | |
| CN114392746B (en) | Magnetic Co-CoFe 2 O 4 /NC-NH 2 Composite catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |