CN109603886B - Fe3O4/g-C3N4Composite materials and their use as catalysts - Google Patents

Fe3O4/g-C3N4Composite materials and their use as catalysts Download PDF

Info

Publication number
CN109603886B
CN109603886B CN201910021316.1A CN201910021316A CN109603886B CN 109603886 B CN109603886 B CN 109603886B CN 201910021316 A CN201910021316 A CN 201910021316A CN 109603886 B CN109603886 B CN 109603886B
Authority
CN
China
Prior art keywords
nickel
composite material
doped
ferrous sulfate
alkali metal
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
Application number
CN201910021316.1A
Other languages
Chinese (zh)
Other versions
CN109603886A (en
Inventor
金卫星
王元有
金党琴
封娜
束影
钱亚兵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangzhou Polytechnic Institute
Original Assignee
Yangzhou Polytechnic Institute
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yangzhou Polytechnic Institute filed Critical Yangzhou Polytechnic Institute
Priority to CN201910021316.1A priority Critical patent/CN109603886B/en
Publication of CN109603886A publication Critical patent/CN109603886A/en
Application granted granted Critical
Publication of CN109603886B publication Critical patent/CN109603886B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to novel Fe3O4/g‑C3N4Composite material and its use as catalyst, said novel Fe3O4/g‑C3N4The preparation method of the composite material comprises the following steps: (1) dissolving ferrous sulfate and polyvinylpyrrolidone in water, heating to 90 ℃, adding an alkali metal hydroxide solution, stirring for 4-5h, naturally cooling to room temperature, filtering, washing precipitates with deionized water, and drying for later use; (2) grinding the precipitate obtained in the step (1), nickel nitrate and melamine uniformly by using a mortar, putting the ground precipitate into a muffle furnace, heating to 500 ℃, preserving heat for 3 hours, and naturally cooling to room temperature to obtain the nickel-doped Fe3O4/g‑C3N4A composite material.

Description

Fe3O4/g-C3N4Composite materials and their use as catalysts
Technical Field
The invention belongs to the field of materials and catalysis, and particularly relates to novel Fe3O4/g-C3N4Composite materials and their use as catalysts.
Background
Graphite phase carbon nitride (g-C)3N4) The structure of the photocatalyst is two-dimensional lamellar, N is used as a heteroatom to carry out conjugated pi bond connection between the layers in the molecule, and the carbon atom is connected with the nitrogen atom by a covalent bond, so that the photocatalyst keeps high stability under the acid-base condition, has a band gap of about 2.7eV, and shows good photocatalytic performance. At present g-C3N4The composite material is mainly used for the fields of hydrogen and oxygen production by photocatalytic hydrolysis, degradation of photocatalytic pollutants, photocatalytic organic synthesis and the like, and has wide application. The inventor previously prepared a SiO by a pyrolysis method2/ZnO/g-C3N4The nano material shows good catalytic activity in the photocatalysis degradation of hexavalent chromium (application number: 201710572468.1), and aims to research g-C3N4The invention provides a nickel-doped novel Fe3O4/g-C3N4Composite materials and their use as catalystsThe use of an agent.
Disclosure of Invention
The invention provides nickel-doped Fe3O4/g-C3N4Composite material, characterized in that the nickel-doped Fe3O4/g-C3N4The preparation method of the composite material comprises the following steps:
(1) dissolving ferrous sulfate and polyvinylpyrrolidone in water, heating to 90 ℃, adding an alkali metal hydroxide solution, stirring for 4-5h, naturally cooling to room temperature, filtering, washing precipitates with deionized water, and drying for later use;
(2) grinding the precipitate obtained in the step (1), nickel nitrate and melamine uniformly by using a mortar, putting the ground precipitate into a muffle furnace, heating to 500 ℃, preserving heat for 3 hours, and naturally cooling to room temperature to obtain the nickel-doped Fe3O4/g-C3N4A composite material.
In the step (1), 10mL of water and 0.2mL of polyvinylpyrrolidone are used per millimole of ferrous sulfate, the alkali metal hydroxide is preferably sodium hydroxide and potassium hydroxide, the concentration of the alkali metal hydroxide solution is preferably 3-5mol/L, and the molar ratio of the ferrous sulfate to the alkali metal hydroxide is 1: 2-3.
The molar dosage of the nickel nitrate in the step (2) is 0.2 times of the dosage of the ferrous sulfate in the step (1), and the molar dosage of the melamine is 3.5-4.0 times of the dosage of the ferrous sulfate in the step (1).
Another embodiment of the present invention provides the above nickel-doped Fe3O4/g-C3N4The composite material is applied to the preparation of 2, 4-dichloroaniline by catalyzing 2, 4-dichloronitrobenzene.
Another embodiment of the present invention provides a method for producing 2, 4-dichloroaniline, comprising the steps of:
dissolving 2, 4-dichloronitrobenzene in absolute ethyl alcohol, adding a catalytic amount of nickel-doped Fe3O4/g-C3N4Composite material of 0.5-1.0MPa H2Under the condition that the reaction temperature is 55-60 ℃ and the reaction time is 5-8h, the 2, 4-dichloroaniline is obtained.
The nickel-doped Fe3O4/g-C3N4The amount of the composite material is preferably 0.1-0.2 g of nickel-doped Fe per gram of 2, 4-dichloronitrobenzene3O4/g-C3N4A composite material.
Compared with the prior art, the invention has the advantages that: the invention provides a brand new nickel-doped Fe3O4/g-C3N4The composite material can be used for preparing 2, 4-dichloroaniline from 2, 4-dichloronitrobenzene by catalytic hydrogenation, and has the advantages of mild reaction conditions, high conversion rate and selectivity and less side reactions.
Drawings
FIG. 1 shows SEM (A) and TEM (B) images of product A.
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1
(1) Dissolving ferrous sulfate (10mmol) and polyvinylpyrrolidone (2mL) in deionized water (100mL), heating to 90 ℃, adding NaOH solution (5mol/L and 4mL), stirring for 5h, naturally cooling to room temperature, filtering, washing precipitate with deionized water, and drying for later use;
(2) uniformly grinding the precipitate obtained in the step (1), nickel nitrate (2mmol) and melamine (35mmol) by using a mortar, putting the mixture into a muffle furnace, heating to 500 ℃, preserving heat for 3 hours, and naturally cooling to room temperature to obtain the nickel-doped Fe3O4/g-C3N4Composite material (hereinafter referred to as product a, fig. 1).
Example 2
(1) Dissolving ferrous sulfate (10mmol) and polyvinylpyrrolidone (2mL) in deionized water (100mL), heating to 90 ℃, adding KOH solution (3mol/L and 10mL), stirring for 4h, naturally cooling to room temperature, filtering, washing precipitate with deionized water, and drying for later use;
(2) uniformly grinding the precipitate obtained in the step (1), nickel nitrate (2mmol) and melamine (40mmol) by using a mortar, putting the mixture into a muffle furnace, heating to 500 ℃, preserving heat for 3 hours, and naturally cooling to room temperature to obtain the nickel-doped Fe3O4/g-C3N4Composite material (hereinafter referred to as product B).
Example 3
2, 4-Dichloronitrobenzene (2.0g) was dissolved in absolute ethanol (40mL) and a catalytic amount of product A (0.2g) was added at 1.0MPa H2Under the conditions that the reaction temperature is 55-60 ℃ and the reaction time is 8h, 2, 4-dichloroaniline is obtained (gas chromatography analysis shows that the conversion rate is 99.83 percent, the selectivity is 100 percent, and no by-product is found).
Example 4
2, 4-Dichloronitrobenzene (2.0g) was dissolved in absolute ethanol (40mL) and a catalytic amount of product B (0.4g) was added at 0.5MPa H2Under the conditions of the reaction temperature of 55-60 ℃ and the reaction time of 5h, 2, 4-dichloroaniline is obtained (gas chromatography analysis shows that the conversion rate is 99.90%, the selectivity is 100%, and no by-product is found).
Example 5
2, 4-Dichloronitrobenzene (2.0g) was dissolved in absolute ethanol (40mL), Raney-Ni (0.2g) was added at 1.0MPa H2Under the conditions of the reaction temperature of 55-60 ℃ and the reaction time of 8h, the conversion rate is 56.34 percent by gas chromatographic analysis, and the selectivity is poor.
Example 6
2, 4-Dichloronitrobenzene (2.0g) was dissolved in toluene (40mL), Raney-Ni (0.2g) was added at 1.0MPa H2Under the conditions that the reaction temperature is 90-95 ℃, and after the reaction time is 8 hours, gas chromatography analysis shows that the conversion rate of 2, 4-dichloroaniline (retention time is 11.40min) is 99.80%, the selectivity is 92.51%, and three byproducts are respectively 2-chloroaniline (retention time is 10.06min, 2.23%), aniline (retention time is 8.62min, 2.81%) and 3-chloro-4-aminophenol (retention time is 11.58min, 2.06%).

Claims (7)

1. Nickel-doped Fe3O4/g-C3N4Composite material, characterized in that the nickel-doped Fe3O4/g-C3N4The preparation method of the composite material comprises the following steps:
(1) dissolving ferrous sulfate and polyvinylpyrrolidone in water, heating to 90 ℃, adding an alkali metal hydroxide solution, stirring for 4-5h, naturally cooling to room temperature, filtering, washing precipitates with deionized water, and drying for later use;
(2) grinding the precipitate obtained in the step (1), nickel nitrate and melamine uniformly by using a mortar, putting the ground precipitate into a muffle furnace, heating to 500 ℃, preserving heat for 3 hours, and naturally cooling to room temperature to obtain the nickel-doped Fe3O4/g-C3N4A composite material.
2. Nickel doped Fe according to claim 13O4/g-C3N4The composite material is characterized in that 10mL of water and 0.2mL of polyvinylpyrrolidone are used per millimole of ferrous sulfate in the step (1).
3. Nickel doped Fe according to any of claims 1-23O4/g-C3N4The composite material is characterized in that the alkali metal hydroxide in the step (1) is sodium hydroxide and potassium hydroxide, the concentration of the alkali metal hydroxide solution is preferably 3-5mol/L, and the molar ratio of ferrous sulfate to the alkali metal hydroxide is 1: 2-3.
4. Nickel doped Fe according to claim 13O4/g-C3N4The composite material is characterized in that the molar amount of the nickel nitrate in the step (2) is 0.2 time of the amount of the ferrous sulfate in the step (1), and the molar amount of the melamine is 3.5-4.0 times of the amount of the ferrous sulfate in the step (1).
5. Nickel doped Fe according to any of claims 1 to 43O4/g-C3N4The composite material is applied to the preparation of 2, 4-dichloroaniline by catalyzing 2, 4-dichloronitrobenzene.
6. The preparation method of 2, 4-dichloroaniline is characterized by comprising the following steps:
dissolving 2, 4-dichloronitrobenzene in absolute ethanol, adding a catalytic amount of nickel-doped Fe as claimed in any of claims 1 to 43O4/g-C3N4Composite material of 0.5-1.0MPa H2Under the condition that the reaction temperature is 55-60 ℃ and the reaction time is 5-8h, the 2, 4-dichloroaniline is obtained.
7. The method of claim 6, wherein the nickel-doped Fe3O4/g-C3N4The dosage of the composite material is 0.1-0.2 g of nickel-doped Fe per gram of 2, 4-dichloronitrobenzene3O4/g-C3N4A composite material.
CN201910021316.1A 2019-01-09 2019-01-09 Fe3O4/g-C3N4Composite materials and their use as catalysts Active CN109603886B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910021316.1A CN109603886B (en) 2019-01-09 2019-01-09 Fe3O4/g-C3N4Composite materials and their use as catalysts

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910021316.1A CN109603886B (en) 2019-01-09 2019-01-09 Fe3O4/g-C3N4Composite materials and their use as catalysts

Publications (2)

Publication Number Publication Date
CN109603886A CN109603886A (en) 2019-04-12
CN109603886B true CN109603886B (en) 2021-12-10

Family

ID=66015697

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910021316.1A Active CN109603886B (en) 2019-01-09 2019-01-09 Fe3O4/g-C3N4Composite materials and their use as catalysts

Country Status (1)

Country Link
CN (1) CN109603886B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113070087B (en) * 2021-04-02 2021-11-19 绍兴绿奕化工有限公司 Non-noble metal catalyst and preparation method and application thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103736514B (en) * 2014-01-08 2015-07-08 阜阳师范学院 Preparation method and application of novel C3N4/ZnO/Fe2O3 composite photocatalyst
CN104923276B (en) * 2015-03-11 2017-12-05 江苏大学 A kind of preparation method of the compound nickel ferrite based magnetic loaded magnetic photocatalytic material of graphite type carbon nitride
US10413966B2 (en) * 2016-06-20 2019-09-17 Baker Hughes, A Ge Company, Llc Nanoparticles having magnetic core encapsulated by carbon shell and composites of the same
CN106861732A (en) * 2017-01-25 2017-06-20 平顶山学院 A kind of boron nickel titanium dioxide/nitridation carbon composite photocatalyst, and application thereof and preparation method
CN107321375A (en) * 2017-07-13 2017-11-07 扬州工业职业技术学院 A kind of SiO2/ZnO/g‑C3N4Nano material and its application in reduction of hexavalent chromium
CN107983391A (en) * 2017-12-14 2018-05-04 河南师范大学 Insoluble magnetic cobalt/defective g-C3N4 composite catalysts and its application in Oxone degrading waste waters are catalyzed
CN108435225B (en) * 2018-03-09 2020-12-11 浙江工业大学 Fe-N/C composite catalyst and preparation method and application thereof
CN108579819B (en) * 2018-05-21 2021-03-19 西南石油大学 Fe3O4N-doped Ni/Zn-MOFs/g-C3N4Preparation method of composite photocatalytic material
CN108906106B (en) * 2018-07-04 2021-08-06 大连理工大学 FeNi/N-C high-dispersion core-shell structure catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN109603886A (en) 2019-04-12

Similar Documents

Publication Publication Date Title
CN111889132B (en) Metal oxide-molecular sieve catalyst, and preparation method and application thereof
CN108380216B (en) Preparation method and application of cobalt-based catalyst for catalyzing carbon dioxide to prepare ethanol
Yang et al. Selective Hydrogenation of Nitroaromatic Compounds with a Nickel-Oxide-Supported Nano-Palladium Catalyst under Ambient Reaction Conditions.
CN109201096B (en) CO2Catalyst for preparing low-carbon mixed alcohol by hydrogenation and application thereof
CN113061122B (en) Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran
CN113398944B (en) Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof
CN107983356B (en) Catalyst for synthesizing higher branched chain alcohol, preparation method and application
CN111992213B (en) Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
CN109603886B (en) Fe3O4/g-C3N4Composite materials and their use as catalysts
CN100358802C (en) Method of preparing carbon nano tube by Ni/RE/Cu catalyst chemical gaseous phase sedimentation
CN109603887B (en) Nickel-doped Fe 3 O 4 /g-C 3 N 4 Preparation method of composite material and application of composite material in catalytic hydrogenation
CN108079994B (en) Method for preparing p-aminophenol by catalytic hydrogenation of p-nitrophenol
CN117181232A (en) CuZnCeO x Preparation of nano rod catalyst and CO under photo-thermal synergistic catalysis 2 Application in reduction
CN110860295A (en) Fe2O3/Sr2FeTaO6-xPhotocatalyst and preparation method and application thereof
CN116273006A (en) Halogen modified nickel-aluminum hydrotalcite, preparation method thereof and application thereof in lignin catalytic hydrogenation
CN1318140C (en) Catalyst for synthesizing low carbon mixed alcohol by synthetic gas and its preparation method
CN106964356B (en) Semiconductor catalyst for light auxiliary catalysis methanol and carbon dioxide Synthesis of dimethyl carbonate
CN111974409A (en) Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof
CN105753717A (en) Application of metal-free hydrogenation catalyst in catalyzing 1-nitronaphthalene hydrogenation reaction
CN115364869B (en) Catalyst for preparing oxalate through CO oxidative coupling, and preparation method and application thereof
CN114345348B (en) Catalyst for preparing isopropanol by acetone hydrogenation and preparation method thereof
CN115155617B (en) Method for efficiently preparing hydrogen from formic acid by quantum dot catalysis and with stable inorganic ligand induced by visible light
CN115739098B (en) Catalyst and preparation method and application thereof
CN109304193B (en) Catalyst for preparing acrolein from glycerin
CN118162194B (en) Catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation 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