CN105858663A - Preparation method of bowl-shaped carbon-molybdenum carbide composite material - Google Patents

Preparation method of bowl-shaped carbon-molybdenum carbide composite material Download PDF

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Publication number
CN105858663A
CN105858663A CN201610400250.3A CN201610400250A CN105858663A CN 105858663 A CN105858663 A CN 105858663A CN 201610400250 A CN201610400250 A CN 201610400250A CN 105858663 A CN105858663 A CN 105858663A
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trimethylammonium bromide
cetyl trimethylammonium
bowl
molybdenum carbide
mol ratio
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CN105858663B (en
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杜建平
王金平
侯小红
赵治军
吴金婷
赵天赐
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Taiyuan University of Technology
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Taiyuan University of Technology
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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
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to the field of catalytic materials, in particular to a preparation method of a bowl-shaped carbon-molybdenum carbide composite material. The preparation method comprises the steps that hexadecyl trimethyl ammonium bromide, silicon dioxide micro-nanospheres, hydroquinone or resorcinol or pyrogallol, a formaldehyde solution, hydrazine hydrate and hydrazine hydrate or phosphomolybdic acid are mixed, stirred, dried and then subjected to calcining and heating treatment, and the composite material is obtained. According to the preparation method of the bowl-shaped carbon-molybdenum carbide composite material, the preparation process is simple, operation is convenient, technological parameters are easy to control, the obtained carbon particles have the bowl-shaped morphology and are uniform in particle size and high in dispersity, and a novel composite material obtained by compounding the carbon particles with molybdenum carbide is expected to be applied to the catalytic field.

Description

A kind of bowl-shape carbon and the preparation method of molybdenum carbide composite
Technical field
The present invention relates to the preparation method of catalysis material field, a kind of bowl-shape carbon and molybdenum carbide composite.
Background technology
Metal carbides are the new function materials that a class has high rigidity, high-melting-point, good thermal stability and corrosion resistance, are applied in many fields.The 90's of 20th century, the report metal carbides such as Ledoux have the characteristic of class noble metal, think in metal carbides, fill between carbon atom in metal lattice, cause the change of electron density, make lattice parameter become big, spacing of lattice increases, thus causing d band to shrink, Fermi's energy state d electron density increases, thus has similar surface nature and absorption characteristic to noble metal.In recent years, carbide especially molybdenum carbide causes extensive concern as a class new catalytic material.For catalysis activity, molybdenum carbide is similar to Pt race noble metal in many aspects, particularly suitable with the noble metal such as Pt, Pd on its hydrogen evolution activity, is expected to become the substitute of noble metal.
Along with going deep into of research, the new method preparing molybdenum carbide is also constantly proposing and checking.At present, the preparation method of molybdenum carbide mainly has following several: (1) temperature-programmed reaction method, by molybdenum oxide precursor at light hydrocarbon or light hydrocarbon/H2Gaseous mixture Program intensification carbonization (TPRe).The method is simply easily empty and product is purer, but the method is easily caused catalyst surface area carbonization, and gained molybdenum carbide specific surface area is less.(2) carbothermic method, is reacted in protective atmosphere or reducing atmosphere by molybdenum oxide and appropriate carbon carrier, and the product that the method obtains has bigger specific surface area, but this reaction temperature is the highest.(3) solvothermal method, the method is to use the material (KBH4) that reducing power is strong that molybdenum oxide is reduced to molybdenum carbide, the method is simple and easy to control, temperature is relatively low, but product is impure, (4) metal precursor cracking process, is to utilize metallo-organic compound and utilize ammonium molybdate to prepare with the mixture Pintsch process of hexamethylenetetramine, but presoma preparation complexity, and prepared granule is bigger.Additionally, the also report such as CVD, hydro-thermal method, ultrasonic method, microwave method, but the problem that to equally exist yield little for these methods, reacts insufficient, product grain is big, product is impure.Above method is limited exists bigger deficiency with feature own in terms of reality applies the volume production of particularly catalyst.
Summary of the invention
It is desirable to provide a kind of NEW TYPE OF COMPOSITE catalysis material, a kind of bowl-shape carbon and the preparation method of molybdenum carbide composite.
The present invention is achieved by the following technical solutions: the preparation method of a kind of bowl-shape carbon and molybdenum carbide composite, and it is through the following steps that realize:
(1) cetyl trimethylammonium bromide is completely dissolved in the mixed liquor of the second alcohol and water that volume ratio is 1:2 the cetyl trimethylammonium bromide solution of formation 0.6～4g/L, add and the silicon dioxide micro-nano ball that cetyl trimethylammonium bromide mol ratio is 0.1～0.6:5～6, after being uniformly dispersed, add and the hydroquinone that cetyl trimethylammonium bromide mol ratio is 0.1～0.6:0.9～2 or resorcinol or pyrogallol, it is subsequently adding formalin, in described formalin, formaldehyde and cetyl trimethylammonium bromide mol ratio are 0.1～0.6:5～10；Add and the hydrazine hydrate that cetyl trimethylammonium bromide mol ratio is 0.1～0.6:7～14, it is eventually adding and the ammonium molybdate that cetyl trimethylammonium bromide mol ratio is 0.1～0.6:1～6 or phosphomolybdic acid, after 15-18h is stirred at room temperature, it is dried to obtain pressed powder；
(2), by the pressed powder that obtains in step (1) 700～900oCalcine 3 hours under C, obtain composite first product；
(3), the primary product that will obtain in step (2), join in 2mol/L sodium hydroxide solution, 100～120oHeat treated 18 hours under C, i.e. obtain bowl-shape carbon and molybdenum carbide composite.
In the present invention, the effect of cetyl trimethylammonium bromide is dispersion and modifies silicon dioxide micro-nano ball；The effect of silicon dioxide micro-nano ball is to serve as template so that it is Surface coating organic reaction product；The effect of hydroquinone (resorcinol or phloroglucinol) and formaldehyde is to serve as reactant, it is provided that the presoma of carbon；The effect of hydrazine hydrate is the alkaline environment providing reaction to need.Wherein cetyl trimethylammonium bromide, silicon dioxide micro-nano ball and post processing (heat treated) make carbon granule form bowl-shape carbon pattern.
A kind of bowl-shape carbon of the present invention and the preparation method of molybdenum carbide composite, preparation process is simple, easy to operate, technological parameter is easily controllable, and the carbon granule obtained has bowl-shape pattern, and epigranular, high degree of dispersion, meets the advanced composite material (ACM) obtained, is expected to be used for catalytic field with molybdenum carbide.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of bowl-shape carbon and the molybdenum carbide composite prepared by the method for the invention.
Fig. 2 is the transmission electron microscope picture of composite.
Fig. 3 is the XRD figure of bowl-shape carbon and the molybdenum carbide composite prepared by the method for the invention.
Detailed description of the invention
Embodiment 1
A kind of preparation method of bowl-shape carbon and molybdenum carbide composite, it is through the following steps that realize:
(1) cetyl trimethylammonium bromide is completely dissolved in the mixed liquor of the second alcohol and water that volume ratio is 1:2 is formed the cetyl trimethylammonium bromide solution of 0.6g/L, add and the silicon dioxide micro-nano ball that cetyl trimethylammonium bromide mol ratio is 0.3:6, after being uniformly dispersed, adding with cetyl trimethylammonium bromide mol ratio is the hydroquinone of 0.1:1.5, being subsequently adding formalin, described cetyl trimethylammonium bromide is 0.6:5 with formaldehyde mole ratio in formalin；Adding with cetyl trimethylammonium bromide mol ratio is the hydrazine hydrate of 0.3:14, and being eventually adding with cetyl trimethylammonium bromide mol ratio is the ammonium molybdate of 0.1:3, after 18h is stirred at room temperature, is dried to obtain pressed powder；
(2), by the pressed powder that obtains in step (1) 700oCalcine 3 hours under C, obtain composite first product；
(3), the primary product that will obtain in step (2), join in 2mol/L sodium hydroxide solution, 110oHeat treated 18 hours under C, i.e. obtain bowl-shape carbon and molybdenum carbide composite.
Embodiment 2
A kind of preparation method of bowl-shape carbon and molybdenum carbide composite, it is through the following steps that realize:
(1) cetyl trimethylammonium bromide is completely dissolved in the mixed liquor of the second alcohol and water that volume ratio is 1:2 is formed the cetyl trimethylammonium bromide solution of 2g/L, add and the silicon dioxide micro-nano ball that cetyl trimethylammonium bromide mol ratio is 0.6:5, after being uniformly dispersed, adding with cetyl trimethylammonium bromide mol ratio is the resorcinol of 0.3:2, being subsequently adding formalin, in described formalin, formaldehyde and cetyl trimethylammonium bromide mol ratio are 0.1:8；Adding with cetyl trimethylammonium bromide mol ratio is the hydrazine hydrate of 0.6:7, and being eventually adding with cetyl trimethylammonium bromide mol ratio is the phosphomolybdic acid of 0.3:6, after 15h is stirred at room temperature, is dried to obtain pressed powder；
(2), by the pressed powder that obtains in step (1) 800oCalcine 3 hours under C, obtain composite first product；
(3), the primary product that will obtain in step (2), join in 2mol/L sodium hydroxide solution, 120oHeat treated 18 hours under C, i.e. obtain bowl-shape carbon and molybdenum carbide composite.
Embodiment 3
A kind of preparation method of bowl-shape carbon and molybdenum carbide composite, it is through the following steps that realize:
(1) cetyl trimethylammonium bromide is completely dissolved in the mixed liquor of the second alcohol and water that volume ratio is 1:2 is formed the cetyl trimethylammonium bromide solution of 4g/L, add and the silicon dioxide micro-nano ball that cetyl trimethylammonium bromide mol ratio is 0.1:5.5, after being uniformly dispersed, adding with cetyl trimethylammonium bromide mol ratio is the pyrogallol of 0.6:0.9, being subsequently adding formalin, in described formalin, formaldehyde and cetyl trimethylammonium bromide mol ratio are 0.3:10；Adding with cetyl trimethylammonium bromide mol ratio is the hydrazine hydrate of 0.1:10, and being eventually adding with cetyl trimethylammonium bromide mol ratio is 0.6:1 phosphomolybdic acid, after 17h is stirred at room temperature, is dried to obtain pressed powder；
(2), by the pressed powder that obtains in step (1) 900oCalcine 3 hours under C, obtain composite first product；
(3), the primary product that will obtain in step (2), join in 2mol/L sodium hydroxide solution, 100oHeat treated 18 hours under C, i.e. obtain bowl-shape carbon and molybdenum carbide composite.

Claims (1)

1. the preparation method of a bowl-shape carbon and molybdenum carbide composite, it is characterised in that it is through the following steps that realize:
(1) cetyl trimethylammonium bromide is completely dissolved in the mixed liquor of the second alcohol and water that volume ratio is 1:2 the cetyl trimethylammonium bromide solution of formation 0.6～4g/L, add and the silicon dioxide micro-nano ball that cetyl trimethylammonium bromide mol ratio is 0.1～0.6:5～6, after being uniformly dispersed, add and the hydroquinone that cetyl trimethylammonium bromide mol ratio is 0.1～0.6:0.9～2 or resorcinol or pyrogallol, it is subsequently adding formalin, in described formalin, formaldehyde and cetyl trimethylammonium bromide mol ratio are 0.1～0.6:5～10；Add and the hydrazine hydrate that cetyl trimethylammonium bromide mol ratio is 0.1～0.6:7～14, it is eventually adding and the ammonium molybdate that cetyl trimethylammonium bromide mol ratio is 0.1～0.6:1～6 or phosphomolybdic acid, after 15-18h is stirred at room temperature, it is dried to obtain pressed powder；
(2), by the pressed powder that obtains in step (1) 700～900oCalcine 3 hours under C, obtain composite first product；
(3), the primary product that will obtain in step (2), join in 2mol/L sodium hydroxide solution, 100～120oHeat treated 18 hours under C, i.e. obtain bowl-shape carbon and molybdenum carbide composite.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110575840A (en) * 2019-09-10 2019-12-17 太原理工大学 Preparation method of two-dimensional molybdenum carbide/graphene nanosheet composite material
CN112591754A (en) * 2020-12-25 2021-04-02 太原理工大学 Preparation method of carbon nanocage coupled molybdenum carbide quantum dot nanocomposite
CN113745010A (en) * 2021-08-11 2021-12-03 上海交通大学 Ternary composite material and preparation method and application thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110575840A (en) * 2019-09-10 2019-12-17 太原理工大学 Preparation method of two-dimensional molybdenum carbide/graphene nanosheet composite material
CN110575840B (en) * 2019-09-10 2022-05-10 太原理工大学 Preparation method of two-dimensional molybdenum carbide/graphene nanosheet composite material
CN112591754A (en) * 2020-12-25 2021-04-02 太原理工大学 Preparation method of carbon nanocage coupled molybdenum carbide quantum dot nanocomposite
CN112591754B (en) * 2020-12-25 2022-07-22 太原理工大学 Preparation method of carbon nanocage coupled molybdenum carbide quantum dot nanocomposite
CN113745010A (en) * 2021-08-11 2021-12-03 上海交通大学 Ternary composite material and preparation method and application thereof

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