CN109603886A - A kind of novel Fe3O4/g-C3N4Composite material and its application as catalyst - Google Patents

A kind of novel Fe3O4/g-C3N4Composite material and its application as catalyst Download PDF

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Publication number
CN109603886A
CN109603886A CN201910021316.1A CN201910021316A CN109603886A CN 109603886 A CN109603886 A CN 109603886A CN 201910021316 A CN201910021316 A CN 201910021316A CN 109603886 A CN109603886 A CN 109603886A
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composite material
nickel
doping
dosage
nickel doping
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CN109603886B (en
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金卫星
王元有
金党琴
封娜
束影
钱亚兵
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Yangzhou Polytechnic Institute
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Yangzhou Polytechnic Institute
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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
    • 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

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  • 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 present invention relates to a kind of novel Fe3O4/g‑C3N4Composite material and its application as catalyst, the novel Fe3O4/g‑C3N4The preparation method of composite material includes the following steps: that (1) is soluble in water by ferrous sulfate, polyvinylpyrrolidone, and after being warming up to 90 DEG C, alkali hydroxide soln is added, after stirring 4-5h, rear drying for standby is washed with deionized in cooled to room temperature, filtering, precipitating；(2) precipitating for obtaining step (1) and nickel nitrate, melamine, with mortar grinder it is uniform after, be put into Muffle furnace, after being warming up to 500 DEG C, heat preservation 3 hours, Fe that cooled to room temperature is adulterated to get the nickel3O4/g‑C3N4Composite material.

Description

A kind of novel Fe3O4/g-C3N4Composite material and its application as catalyst
Technical field
The invention belongs to material and catalytic fields, and in particular to a kind of novel Fe3O4/g-C3N4Composite material and its conduct The application of catalyst.
Background technique
Graphite phase carbon nitride (g-C3N4) structure be two-dimensional layer, portion's interlayer is conjugated by hetero atom of N in the molecule Pi bond connection, is attached between carbon atom and nitrogen-atoms by covalent bond, so that it is kept very high stabilization under acid-base condition Property, band gap ≈ 2.7eV shows good photocatalysis performance.G-C at present3N4And its composite material is mainly used for photocatalysis hydrolysis The fields such as hydrogen and oxygen production, the degradation of photocatalysis pollutant, photocatalysis organic synthesis are all widely used.Prior inventions people uses Pyrolysismethod is prepared for a kind of SiO2/ZnO/g-C3N4Nano material shows good catalysis in photocatalytic degradation Cr VI Activity (application number: 201710572468.1), for further research g-C3N4Composite catalyst, the present invention provide a kind of nickel The novel Fe of doping3O4/g-C3N4Composite material and its application as catalyst.
Summary of the invention
The present invention provides a kind of Fe of nickel doping3O4/g-C3N4Composite material, it is characterised in that the Fe of the nickel doping3O4/ g-C3N4The preparation method of composite material includes the following steps:
(1) ferrous sulfate, polyvinylpyrrolidone is soluble in water, after being warming up to 90 DEG C, alkali metal hydroxide is added Solution, after stirring 4-5h, cooled to room temperature, filtering precipitates and rear drying for standby is washed with deionized；
(2) precipitating for obtaining step (1) and nickel nitrate, melamine, with mortar grinder it is uniform after, be put into Muffle furnace In, it is warming up to 500 DEG C, after heat preservation 3 hours, Fe that cooled to room temperature is adulterated to get the nickel3O4/g-C3N4Composite wood Material.
Every mM of ferrous sulfate uses water 10mL, polyvinylpyrrolidone 0.2mL, the alkali metal hydrogen in step (1) The preferred sodium hydroxide of oxide, potassium hydroxide, the preferred 3-5mol/L of the concentration of alkali hydroxide soln, ferrous sulfate and alkali The molar ratio of metal hydroxides is 1:2-3.
The mole dosage of nickel nitrate is 0.2 times of ferrous sulfate dosage in step (1) in step (2), melamine rubs Your dosage is 3.5-4.0 times of ferrous sulfate dosage in step (1).
Another embodiment of the present invention provides the Fe of above-mentioned nickel doping3O4/g-C3N4Composite material is in catalysis 2,4- dichloro Nitrobenzene prepares the application in 2,4 dichloro aniline.
Another embodiment of the present invention provides the preparation method of one kind 2,4- dichloroaniline, it is characterised in that including as follows Step:
2,4- dichloronitrobenzenes are dissolved in dehydrated alcohol, and the Fe of the nickel doping of catalytic amount is added3O4/g-C3N4Composite material, In 0.5-1.0Mpa H2Under the conditions of, 55-60 DEG C of reaction temperature, reaction time 5-8h is to get 2,4- dichloroaniline.
The Fe of the nickel doping3O4/g-C3N4The dosage of composite material is preferably that every gram of 2,4- dichloronitrobenzene uses 0.1- The Fe of 0.2 gram of nickel doping3O4/g-C3N4Composite material.
Compared with the prior art, the advantages of the present invention are as follows: the present invention provides a kind of Fe of completely new nickel doping3O4/g- C3N4Composite material, the material can be used for catalytic hydrogenation and prepare 2,4- dichloroaniline, reaction condition temperature by 2,4- dichloronitrobenzene Higher with, conversion ratio, selectivity, side reaction is few.
Detailed description of the invention
Fig. 1 is the SEM (A) and TEM (B) figure of product A.
Specific embodiment
For the ease of a further understanding of the present invention, examples provided below has done more detailed description to it.But It is that these embodiments are only not supposed to be a limitation to the present invention or implementation principle for better understanding invention, reality of the invention The mode of applying is not limited to the following contents.
Embodiment 1
(1) ferrous sulfate (10mmol), polyvinylpyrrolidone (2mL) are dissolved in deionized water (100mL), are warming up to It after 90 DEG C, is added NaOH solution (5mol/L, 4mL), after stirring 5h, cooled to room temperature is filtered, and precipitating is washed with deionized water Wash rear drying for standby；
(2) precipitating for obtaining step (1) and nickel nitrate (2mmol), melamine (35mmol), it is uniform with mortar grinder Afterwards, it is put into Muffle furnace, is warming up to 500 DEG C, after heat preservation 3 hours, Fe that cooled to room temperature is adulterated to get the nickel3O4/ g-C3N4Composite material (hereinafter referred to as product A, Fig. 1).
Embodiment 2
(1) ferrous sulfate (10mmol), polyvinylpyrrolidone (2mL) are dissolved in deionized water (100mL), are warming up to It after 90 DEG C, is added KOH solution (3mol/L, 10mL), after stirring 4h, cooled to room temperature is filtered, and precipitating is washed with deionized water Wash rear drying for standby；
(2) precipitating for obtaining step (1) and nickel nitrate (2mmol), melamine (40mmol), it is uniform with mortar grinder Afterwards, it is put into Muffle furnace, is warming up to 500 DEG C, after heat preservation 3 hours, Fe that cooled to room temperature is adulterated to get the nickel3O4/ g-C3N4Composite material (hereinafter referred to as product B).
Embodiment 3
2,4- dichloronitrobenzenes (2.0g) are dissolved in dehydrated alcohol (40mL), and the product A (0.2g) of catalytic amount is added, 1.0Mpa H2Under the conditions of, 55-60 DEG C of reaction temperature, up to 2,4- dichloroaniline, (gas chromatographic analysis turns after reaction time 8h Rate is 99.83%, and selectivity 100% does not find by-product).
Embodiment 4
2,4- dichloronitrobenzenes (2.0g) are dissolved in dehydrated alcohol (40mL), and the product B (0.4g) of catalytic amount is added, 0.5Mpa H2Under the conditions of, 55-60 DEG C of reaction temperature, up to 2,4- dichloroaniline, (gas chromatographic analysis turns after reaction time 5h Rate is 99.90%, and selectivity 100% does not find by-product).
Embodiment 5
2,4- dichloronitrobenzenes (2.0g) are dissolved in dehydrated alcohol (40mL), are added Raney-Ni (0.2g), in 1.0Mpa H2Under the conditions of, 55-60 DEG C of reaction temperature, after reaction time 8h, gas chromatographic analysis, conversion ratio 56.34%, poor selectivity.
Embodiment 6
2,4- dichloronitrobenzenes (2.0g) are dissolved in toluene (40mL), are added Raney-Ni (0.2g), in 1.0Mpa H2Item Under part, 90-95 DEG C of reaction temperature, after reaction time 8h, gas chromatographic analysis, 2,4- dichloroanilines (retention time 11.40min) Conversion ratio be 99.80%, selectivity 92.51%, it is found that three by-products are 2- chloroaniline (retention time respectively 10.06min, 2.23%), aniline (retention time 8.62min, 2.81%), the chloro- 4-aminophenol (retention time of 3- 11.58min 2.06%).

Claims (7)

1. a kind of Fe of nickel doping3O4/g-C3N4Composite material, it is characterised in that the Fe of the nickel doping3O4/g-C3N4Composite wood The preparation method of material includes the following steps:
(1) ferrous sulfate, polyvinylpyrrolidone is soluble in water, after being warming up to 90 DEG C, alkali hydroxide soln is added, After stirring 4-5h, cooled to room temperature, filtering precipitates and rear drying for standby is washed with deionized；
(2) precipitating for obtaining step (1) and nickel nitrate, melamine, with mortar grinder it is uniform after, be put into Muffle furnace, rise Temperature is to 500 DEG C, after heat preservation 3 hours, Fe that cooled to room temperature is adulterated to get the nickel3O4/g-C3N4Composite material.
2. the Fe of nickel doping described in claim 13O4/g-C3N4Composite material, it is characterised in that every mM of sulphur in step (1) Sour ferrous iron uses water 10mL, polyvinylpyrrolidone 0.2mL.
3. the Fe of the described in any item nickel doping of claim 1-23O4/g-C3N4Composite material, it is characterised in that institute in step (1) State the preferred sodium hydroxide of alkali metal hydroxide, potassium hydroxide, the preferred 3-5mol/L of the concentration of alkali hydroxide soln, sulphur The sour ferrous molar ratio with alkali metal hydroxide is 1:2-3.
4. the Fe of the described in any item nickel doping of claim 1-33O4/g-C3N4Composite material, it is characterised in that nitre in step (2) The mole dosage of sour nickel is 0.2 times of ferrous sulfate dosage in step (1), the mole dosage of melamine is sulphur in step (1) 3.5-4.0 times of sour ferrous iron dosage.
5. the Fe of the described in any item nickel doping of claim 1-43O4/g-C3N4Composite material is in catalysis 2,4- dichloronitrobenzene system Application in standby 2,4 dichloro aniline.
6. one kind 2, the preparation method of 4- dichloroaniline, it is characterised in that include the following steps:
2,4- dichloronitrobenzene is dissolved in dehydrated alcohol, the described in any item nickel doping of claim 1-4 of catalytic amount are added Fe3O4/g-C3N4Composite material, in 0.5-1.0Mpa H2Under the conditions of, 55-60 DEG C of reaction temperature, reaction time 5-8h to get 2,4 dichloro aniline.
7. preparation method as claimed in claim 6, it is characterised in that the Fe of the nickel doping3O4/g-C3N4The dosage of composite material The Fe that preferably every gram of 2,4- dichloronitrobenzene uses 0.1-0.2 grams of nickel to adulterate3O4/g-C3N4Composite material.
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CN113070087A (en) * 2021-04-02 2021-07-06 绍兴绿奕化工有限公司 Non-noble metal catalyst and preparation method and application thereof

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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
CN108435225A (en) * 2018-03-09 2018-08-24 浙江工业大学 A kind of Fe-N/C composite catalysts and its preparation method and application
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CN104923276A (en) * 2015-03-11 2015-09-23 江苏大学 Preparation method of graphite-type carbon nitride composite nickel ferrite magnetic photocatalytic material
US20170361376A1 (en) * 2016-06-20 2017-12-21 Baker Hughes Incorporated Hybrid Fluorescence Magnetic Core-Shell Nanoparticles for Use in Oil and Gas Applications
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
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113070087A (en) * 2021-04-02 2021-07-06 绍兴绿奕化工有限公司 Non-noble metal catalyst and preparation method and application thereof
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

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