CN105858663B - A kind of preparation method of bowl-shape carbon and carbonization molybdenum composite material - Google Patents
A kind of preparation method of bowl-shape carbon and carbonization molybdenum composite material Download PDFInfo
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- CN105858663B CN105858663B CN201610400250.3A CN201610400250A CN105858663B CN 105858663 B CN105858663 B CN 105858663B CN 201610400250 A CN201610400250 A CN 201610400250A CN 105858663 B CN105858663 B CN 105858663B
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- cetyl trimethylammonium
- trimethylammonium bromide
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- 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
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- 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
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- 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
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- 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
Abstract
The present invention relates to catalysis material field, the preparation method of specifically a kind of bowl-shape carbon and carbonization molybdenum composite material, its step is：By cetyl trimethylammonium bromide and silica micro-nano ball, hydroquinones or resorcinol or pyrogallol, formalin, hydrazine hydrate and ammonium molybdate or phosphomolybdic acid, mix, dry, then through calcining and heating, obtain composite.The preparation method of a kind of bowl-shape carbon of the present invention and carbonization molybdenum composite material, preparation process is simple, easy to operate, technological parameter is easily controllable, and obtained carbon particle has bowl-shape pattern, and epigranular, high degree of dispersion, meet obtained advanced composite material (ACM) with molybdenum carbide, be expected to be used for catalytic field.
Description
Technical field
The present invention relates to catalysis material field, the preparation method of specifically a kind of bowl-shape carbon and carbonization molybdenum composite material.
Background technology
Metal carbides are a kind of new function materials with high rigidity, high-melting-point, good thermal stability and corrosion resistance
Material, is applied in many fields.The report metal carbides such as the 90's of 20th century, Ledoux have class noble metal
Characteristic, it is believed that in metal carbides, filled between carbon atom in metal lattice, cause the change of electron density, make lattice parameter
Become big, spacing of lattice increase, so as to cause d bands to shrink, the increase of Fermi energy state d electron densities, thus have to noble metal similar
Surface nature and absorption characteristic.In recent years, carbide especially molybdenum carbide causes extensive concern as a kind of new catalytic material.
For catalytic activity, molybdenum carbide is similar to Pt races noble metals in many aspects, particularly expensive with Pt, Pd etc. on its hydrogen evolution activity
Metal phase is worked as, and is expected to the substitute as noble metal.
With going deep into for research, the new method for preparing molybdenum carbide is also proposed and verified continuous.At present, the system of molybdenum carbide
Preparation Method mainly has following several：(1) temperature-programmed reaction method, by molybdenum oxide precursor in light hydrocarbon or light hydrocarbon/H2It is mixed
Close gas Program heating carbonization (TPRe).This method is simple easily empty and product is purer, but this method is easily caused catalyst surface area
Carbonization, and gained molybdenum carbide specific surface area is smaller.(2) carbothermic method, by molybdenum oxide and appropriate carbon carrier in protection gas
Reacted in atmosphere or reducing atmosphere, the product that this method obtains has a larger specific surface area, but the reaction temperature generally compared with
It is high.(3) solvothermal method, this method are that molybdenum oxide is reduced into molybdenum carbide using reducing power strong material (KBH4), should
Method is simple and easy to control, and temperature is relatively low, but product is impure, (4) metal precursor cracking process, be using metallo-organic compound and
Be made using the mixture Pintsch process of ammonium molybdate and hexamethylenetetramine, but presoma prepare it is complicated, and be made particle compared with
Greatly.In addition, also CVD, hydro-thermal method, ultrasonic method, microwave method etc. are reported, but to equally exist yield small for these methods, and reaction is not
Fully, the problem of product grain is big, product is impure.More than method limited be particularly catalyzed in practical application with feature itself
Larger deficiency be present in terms of the volume production of agent.
The content of the invention
The present invention is intended to provide a kind of NEW TYPE OF COMPOSITE catalysis material, specifically a kind of bowl-shape carbon and carbonization molybdenum composite material
Preparation method.
The present invention is achieved by the following technical solutions：A kind of preparation method of bowl-shape carbon and carbonization molybdenum composite material,
Itself through the following steps that realize：
（1）Cetyl trimethylammonium bromide is completely dissolved in volume ratio as 1:Shape in the mixed liquor of 2 second alcohol and water
Into 0.6~4g/L cetyl trimethylammonium bromide solution, add with cetyl trimethylammonium bromide mol ratio be 0.1~
0.6：5~6 silica micro-nano ball, after being uniformly dispersed, add with cetyl trimethylammonium bromide mol ratio be 0.1~
0.6：0.9~2 hydroquinones or resorcinol or pyrogallol, then adds formalin, formaldehyde in the formalin
It is 0.1~0.6 with cetyl trimethylammonium bromide mol ratio：5~10；Add and cetyl trimethylammonium bromide mole
Than for 0.1~0.6：7~14 hydrazine hydrate, it is 0.1~0.6 to be eventually adding with cetyl trimethylammonium bromide mol ratio：1~
6 ammonium molybdate or phosphomolybdic acid, after 15-18h is stirred at room temperature, is dried to obtain solid powder；
（2）, by step（1）In obtained solid powder 700~900oCalcined 3 hours under C, at the beginning of obtaining composite
Product；
（3）, by step（2）In obtained primary product, be added in 2mol/L sodium hydroxide solutions, 100~120oC
It is lower to heat 18 hours, that is, obtain bowl-shape carbon and carbonization molybdenum composite material.
The effect of cetyl trimethylammonium bromide is scattered and modifies silica micro-nano ball in the present invention；Dioxy
The effect of SiClx micro-nano ball is to serve as template, makes its Surface coating organic reaction product；Hydroquinones（Resorcinol or
Phloroglucin）Effect with formaldehyde is to serve as reactant, there is provided the presoma of carbon；The effect of hydrazine hydrate is that providing reaction needs
The alkaline environment wanted.Wherein cetyl trimethylammonium bromide, silica micro-nano ball and post processing（Heat）So that
Carbon particle forms bowl-shape carbon pattern.
The preparation method of a kind of bowl-shape carbon of the present invention and carbonization molybdenum composite material, preparation process is simple, easy to operate,
Technological parameter is easily controllable, and obtained carbon particle has bowl-shape pattern, and epigranular, high degree of dispersion, meets with molybdenum carbide
The advanced composite material (ACM) arrived, is expected to be used for catalytic field.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph by the bowl-shape carbon that the method for the invention prepares and carbonization molybdenum composite material.
Fig. 2 is the transmission electron microscope picture of composite.
Fig. 3 is the XRD by the bowl-shape carbon that the method for the invention prepares and carbonization molybdenum composite material.
Embodiment
Embodiment 1
A kind of bowl-shape carbon with carbonization molybdenum composite material preparation method, itself through the following steps that realize：
（1）Cetyl trimethylammonium bromide is completely dissolved in volume ratio as 1:Shape in the mixed liquor of 2 second alcohol and water
Into 0.6g/L cetyl trimethylammonium bromide solution, it is 0.3 to add with cetyl trimethylammonium bromide mol ratio：6
Silica micro-nano ball, after being uniformly dispersed, it is 0.1 to add with cetyl trimethylammonium bromide mol ratio：1.5 to benzene two
Phenol, then adds formalin, and the cetyl trimethylammonium bromide is 0.6 with formaldehyde mole ratio in formalin：5；Again
It is 0.3 to add with cetyl trimethylammonium bromide mol ratio：14 hydrazine hydrate, it is eventually adding and cetyl trimethyl bromination
Ammonium mol ratio is 0.1：3 ammonium molybdate, after 18h is stirred at room temperature, it is dried to obtain solid powder；
（2）, by step（1）In obtained solid powder 700oCalcined 3 hours under C, obtain composite first product；
（3）, by step（2）In obtained primary product, be added in 2mol/L sodium hydroxide solutions, 110oAdd under C
Heat treatment 18 hours, that is, obtain bowl-shape carbon and carbonization molybdenum composite material.
Embodiment 2
A kind of bowl-shape carbon with carbonization molybdenum composite material preparation method, itself through the following steps that realize：
（1）Cetyl trimethylammonium bromide is completely dissolved in volume ratio as 1:Shape in the mixed liquor of 2 second alcohol and water
Into 2g/L cetyl trimethylammonium bromide solution, it is 0.6 to add with cetyl trimethylammonium bromide mol ratio：The two of 5
Silica micro-nano ball, after being uniformly dispersed, it is 0.3 to add with cetyl trimethylammonium bromide mol ratio：2 resorcinol,
Then formalin is added, formaldehyde and cetyl trimethylammonium bromide mol ratio are 0.1 in the formalin：8；Add
It is 0.6 with cetyl trimethylammonium bromide mol ratio：7 hydrazine hydrate, is eventually adding and is rubbed with cetyl trimethylammonium bromide
You are than being 0.3：6 phosphomolybdic acid, after 15h is stirred at room temperature, it is dried to obtain solid powder；
（2）, by step（1）In obtained solid powder 800oCalcined 3 hours under C, obtain composite first product；
（3）, by step（2）In obtained primary product, be added in 2mol/L sodium hydroxide solutions, 120oAdd under C
Heat treatment 18 hours, that is, obtain bowl-shape carbon and carbonization molybdenum composite material.
Embodiment 3
A kind of bowl-shape carbon with carbonization molybdenum composite material preparation method, itself through the following steps that realize：
（1）Cetyl trimethylammonium bromide is completely dissolved in volume ratio as 1:Shape in the mixed liquor of 2 second alcohol and water
Into 4g/L cetyl trimethylammonium bromide solution, it is 0.1 to add with cetyl trimethylammonium bromide mol ratio：5.5
Silica micro-nano ball, after being uniformly dispersed, it is 0.6 to add with cetyl trimethylammonium bromide mol ratio：0.9 adjacent benzene three
Phenol, then adds formalin, and formaldehyde and cetyl trimethylammonium bromide mol ratio are 0.3 in the formalin：10；Again
It is 0.1 to add with cetyl trimethylammonium bromide mol ratio：10 hydrazine hydrate, it is eventually adding and cetyl trimethyl bromination
Ammonium mol ratio is 0.6：1 phosphomolybdic acid, after 17h is stirred at room temperature, it is dried to obtain solid powder；
（2）, by step（1）In obtained solid powder 900oCalcined 3 hours under C, obtain composite first product；
（3）, by step（2）In obtained primary product, be added in 2mol/L sodium hydroxide solutions, 100oAdd under C
Heat treatment 18 hours, that is, obtain bowl-shape carbon and carbonization molybdenum composite material.
Claims (1)
1. a kind of bowl-shape carbon with carbonization molybdenum composite material preparation method, it is characterised in that itself through the following steps that realize：
（1）Cetyl trimethylammonium bromide is completely dissolved in volume ratio as 1:0.6 is formed in the mixed liquor of 2 second alcohol and water
~4g/L cetyl trimethylammonium bromide solution, it is 0.1~0.6 to add with cetyl trimethylammonium bromide mol ratio：5
~6 silica micro-nano ball, after being uniformly dispersed, it is 0.1~0.6 to add with cetyl trimethylammonium bromide mol ratio：
0.9~2 hydroquinones or resorcinol or pyrogallol, then adds formalin, formaldehyde and ten in the formalin
Six alkyl trimethyl ammonium bromide mol ratios are 0.1~0.6：5~10；Add and be with cetyl trimethylammonium bromide mol ratio
0.1~0.6：7~14 hydrazine hydrate, it is 0.1~0.6 to be eventually adding with cetyl trimethylammonium bromide mol ratio：1~6
Ammonium molybdate or phosphomolybdic acid, after 15-18h is stirred at room temperature, it is dried to obtain solid powder；
（2）, by step（1）In obtained solid powder 700~900oCalcined 3 hours under C, obtain composite first product；
（3）, by step（2）In obtained primary product, be added in 2mol/L sodium hydroxide solutions, 100~120oAdd under C
Heat treatment 18 hours, that is, obtain bowl-shape carbon and carbonization molybdenum composite material.
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN113745010B (en) * | 2021-08-11 | 2023-01-31 | 上海交通大学 | Ternary composite material and preparation method and application thereof |
Citations (5)
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| CN101869853A (en) * | 2010-05-28 | 2010-10-27 | 中山大学 | Ordered mesoporous carbon/tungsten carbide composite material and supported catalyst thereof and preparation method thereof |
| CN102600876A (en) * | 2010-12-17 | 2012-07-25 | 太原理工大学 | Preparation method of carbon onion loaded transition metal carbide nano composite |
| CN102658187A (en) * | 2012-05-10 | 2012-09-12 | 中南林业科技大学 | Method for preparing vermicular mesoporous tungsten carbide/charcoal composite material |
| CN104743542A (en) * | 2014-11-05 | 2015-07-01 | 北京化工大学 | Hollow mesoporous carbon ball and preparation method thereof |
| CN105217633A (en) * | 2015-09-09 | 2016-01-06 | 四川理工学院 | A kind of preparation method with the nano silicon carbide two molybdenum sheet sprills of regular hexagon structure |
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|---|---|---|---|---|
| CN101869853A (en) * | 2010-05-28 | 2010-10-27 | 中山大学 | Ordered mesoporous carbon/tungsten carbide composite material and supported catalyst thereof and preparation method thereof |
| CN102600876A (en) * | 2010-12-17 | 2012-07-25 | 太原理工大学 | Preparation method of carbon onion loaded transition metal carbide nano composite |
| CN102658187A (en) * | 2012-05-10 | 2012-09-12 | 中南林业科技大学 | Method for preparing vermicular mesoporous tungsten carbide/charcoal composite material |
| CN104743542A (en) * | 2014-11-05 | 2015-07-01 | 北京化工大学 | Hollow mesoporous carbon ball and preparation method thereof |
| CN105217633A (en) * | 2015-09-09 | 2016-01-06 | 四川理工学院 | A kind of preparation method with the nano silicon carbide two molybdenum sheet sprills of regular hexagon structure |
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