CN106861672A - The mesoporous carbon or mesoporous polymer material preparation method of a kind of tungsten functionalization - Google Patents
The mesoporous carbon or mesoporous polymer material preparation method of a kind of tungsten functionalization Download PDFInfo
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- CN106861672A CN106861672A CN201510917413.0A CN201510917413A CN106861672A CN 106861672 A CN106861672 A CN 106861672A CN 201510917413 A CN201510917413 A CN 201510917413A CN 106861672 A CN106861672 A CN 106861672A
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- tungsten
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- Inorganic Chemistry (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to the ordered mesoporous polymer and the synthetic method of ordered mesoporous carbon material of a kind of tungsten functionalization：Reacted with oligomeric phenolic resin and tungsten source, obtain the modified charcoal precursor of tungsten；And by the hydrogen bond action between the precursor and nonionic surfactant and the inductive effect of solution evaporation self assembly, obtain the composite with different mesoscopic structures.The composite is calcined under an inert atmosphere, high temperature carbonization is eventually converted into a series of ordered mesoporous carbon/ordered mesoporous polymer composite of tungsten functionalization.It is this that the characteristics of being modified and have the degree of order high, small tungsten carbide particle and high degree of dispersion by the mesoporous composite material that solution evaporation-induced self-assembly method is obtained is implemented to charcoal precursor；And it is expected to develop other metals or the compound ordered mesoporous carbon/ordered mesoporous polymer material of metal carbides.
Description
Technical field
The present invention relates to the mesoporous carbon or mesoporous polymer material preparation method of a kind of tungsten functionalization.
Background technology
Carbon Materials play important as main catalyst carrier and electrode material in energy conversion, storage and regeneration
Effect；And one of species that tungsten enriches as variable valence, its oxidation state has excellent photolytic activity, its metallic state and carbonization
Thing has and d tracks as precious metal, and then with the property of class noble metal.Therefore, meso-porous carbon material is carried out the work(of tungsten
Energyization, and it is aided with appropriate post processing mode, will be answered with important in catalytic field, electrochemical field and Optical Electro-Chemistry field
Use potentiality.
At present, the tungsten functionalization of mesoporous carbon is mainly to be post-processed by finished product mesoporous carbon (such as impregnate) and obtains.
The mesoporous carbon that this method is obtained carries tungsten oxide/tungsten carbide less stable, is lost in during the course of the reaction serious；And gained tungsten
Species bad dispersibility, grain size distribution is big, and average grain diameter is in 20-50nm.The present invention introduces tungsten while synthesising mesoporous carbon,
The purpose of stabilization tungsten in carbonisation is realized by the chemical action of tungsten and carbon, the tungsten work(of uniform particle diameter, high degree of dispersion is obtained
The ordered mesoporous carbon of energyization/ordered mesoporous polymer material
The content of the invention
It is an object of the invention to provide a kind of ordered mesoporous carbon of tungsten functionalization/ordered mesoporous polymer material.
To achieve the above object, the present invention is implemented using following technical scheme：
In the basic conditions, the resol of pre-polymerization is synthesized.After vacuum dehydration, wolframic acid is added, be brought rapidly up to ＞ 98
Degree, dehydration polymerization obtains the low order phenolic resin of tungsten functionalization.Modified phenolic resin passes through with nonionic surfactant F127
Self assembly is acted on, and prepares the functional mesoporous carbon material of tungsten of with mesoscopic structure, high dispersive；Wherein gained is functional mesoporous
The W content of carbon material is adjustable in 0.01%-40%.
Specific operation process is as follows,
(1) NaOH is added in phenol, the mixed solution of formaldehyde, is warming up to 70 degree, stirred 1 hour or so.In reactant
Hydrochloric acid is added in system, pH is neutralized to for 5-7, water-soluble resin and wolframic acid are mixed, heating makes it fully react to obtain tungsten and be modified
Phenolic resin.Vacuum distillation is removed wherein after moisture, is dissolved in ethanol, be diluted to polymer concentration for 10~
40%.The mass ratio of wherein each reactant：
Phenol：Formaldehyde：Wolframic acid：=1：0.3~3：0.05~0.5
(2) the ethanol solution B of F127 is configured, and is sufficiently mixed with solution A.Resulting solution coated plate, stands, to be evaporated from group
It is carbonized after dress, under inert atmosphere and removes template.
(3) inert gas is nitrogen or argon gas, and the carbonization heating rate is 1~5 DEG C/min.Carbonization temperature exists
At 350~600 degree, the mesoporous polymer material of tungsten functionalization is obtained；During 600 degree to 3000 degree of carbonization temperature ＞, tungsten work(is obtained
The mesoporous carbon material of energyization.
Brief description of the drawings
Fig. 1 wolframic acids are the precursor of tungsten, 900 degree of small angle XRD of carbonization 2 hours.
Fig. 2 wolframic acids are the precursor of tungsten, 900 degree of wide-angle XRD of carbonization 2 hours.
Fig. 3 wolframic acids are the precursor of tungsten, 900 degree of N of carbonization 2 hours2Physical absorption.
Fig. 4 wolframic acids are the precursor of tungsten, 900 degree of pore-size distributions of carbonization 2 hours.
Fig. 5 F127:Resol=0.5:Material TEM when 1.
Fig. 6 F127:Resol=1:Material TEM when 1.
Fig. 7 hydrazine decomposition reaction procatalysts TEM.
Fig. 8 hydrazine decomposition reaction rear catalysts TEM.
Specific embodiment
Embodiment 1：
Under 50 degree, 21g phenol, 22g (37%) formaldehyde and 25% NaOH solution are mixed.It is warming up to 70 degree, stirring 1
Hour.It is cooled to room temperature.Hydrochloric acid is added, after neutralization pH value of solution to 7, is added be followed successively by 0.03 with phenol mol ratios in the solution,
0.06,0.09,0.12 wolframic acid, and reacted 0.5 hour at 100 degree.Afterwards, the F127 ethanol solutions with 20% press F127：It is poly-
Compound mass ratio is 1：1 mixing, is carbonized 2 hours in 900 degree of nitrogen.
Product characteristicses are：
Embodiment 2：
(the wolframic acid on the basis of embodiment 1：Phenol=0.06), change the ratio of F127 and polymer quality, obtain material
Property is：
Embodiment 3：
Gained catalyst is used for hydrazine and decomposes catalytic reaction.Conversion ratio reaches 95% at 30 degree, and conversion ratio reaches at 60 degree
100%.
Claims (9)
1. a kind of mesoporous carbon or mesoporous polymer material preparation method of tungsten functionalization, the method is as follows：
The presoma of water-soluble resin and tungsten is mixed, heating makes it fully react to obtain the modified phenolic resin of tungsten；Gained tree
Fat is neutralized to pH for 5-7, and vacuum distillation is removed after wherein moisture, is dissolved in obtaining solution A in organic solvent, and with it is molten
The solution B for having nonionic surfactant is sufficiently mixed；After treating that solvent evaporates, by gained mixture hot setting, in inertia
Pyrolysis charring in atmosphere, prepares the mesoporous polymer or mesoporous carbon material of tungsten functionalization.
2. according to the preparation method described in claim 1, it is characterised in that：The synthetic method of the tungsten phenol-formaldehyde resin modified is such as
Under：
First in organic solvent, 60-80 DEG C is reacted 30-90 minutes, adds contain afterwards by phenol and formaldehyde in the basic conditions
The presoma of tungsten, reacts 30-90 minutes at 80-100 DEG C, obtains the modified high molecular weight water soluble polymer of tungsten.
3. according to the preparation method described in claim 2, it is characterised in that：
1) alkalescence condition is to add NaOH, potassium hydroxide, ammoniacal liquor, one or two or more kinds in urea；System pH
It is 9-12；
2) presoma of the tungstenic is one or two or more kinds in wolframic acid, phosphotungstic acid, metatungstic acid ammonia；
3) mole ratio of the molal quantity and phenol that add tungsten is 0.0001-0.3；The mole ratio of phenol and formaldehyde is 1:
0.8-3；
4) organic solvent is one or two or more kinds in methyl alcohol, ethanol or acetone.
4. according to the preparation method described in claim 3, it is characterised in that：
1) alkalescence condition is addition NaOH；
2) presoma of the tungstenic is one or two or more kinds in wolframic acid, metatungstic acid ammonia；
3) mole ratio of the molal quantity and phenol that add tungsten is 0.0001-0.15.
5. according to preparation method described in claim 1, it is characterised in that：The preparation process of solution A,
1) neutrality condition is to add hydrochloric acid, acetic acid, one or two or more kinds in citric acid；
2) organic solvent is one or two or more kinds in methyl alcohol, ethanol or acetone, the modified phenolic resin of tungsten in solution A
Mass concentration 1%-60%.
6. according to preparation method described in claim 1, it is characterised in that：The preparation process of solution B, using organic solvent and go from
The mixed solvent of sub- water；The volume ratio 1 of organic solvent and deionized water:0.01-2；The mass concentration of nonionic surfactant
0.5%-40%.1) nonionic surfactant is one or two or more kinds in F127, F108 or P123；
2) organic solvent is one or two or more kinds in methyl alcohol, ethanol or acetone.
7. according to preparation method described in claim 1 or 6, it is characterised in that：The modified phenolic resin of the tungsten and nonionic table
The mass ratio of face activating agent is 1-5.
8. according to preparation method described in claim 1, it is characterised in that：The solidification temperature is 80-120 DEG C, and the time is 8-48
Hour.
9. according to preparation method described in claim 1, it is characterised in that：
1) inert gas is nitrogen or argon gas, and the carbonization heating rate is 1-5 DEG C/min from room temperature to charing temperature
Degree；Carbonization time 2-10 hours
2) carbonization temperature obtains the mesoporous polymer material of tungsten functionalization at 350-600 DEG C；
2) during 600 DEG C to 3000 DEG C of carbonization temperature ＞, the mesoporous carbon material of tungsten functionalization is obtained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108480655A (en) * | 2018-04-10 | 2018-09-04 | 河南大学 | A kind of carbon-supported metal tungsten nano particle |
| CN108500282A (en) * | 2018-04-10 | 2018-09-07 | 河南大学 | A kind of preparation method of carbon-supported metal tungsten nano particle |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2015
- 2015-12-11 CN CN201510917413.0A patent/CN106861672A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108480655A (en) * | 2018-04-10 | 2018-09-04 | 河南大学 | A kind of carbon-supported metal tungsten nano particle |
| CN108500282A (en) * | 2018-04-10 | 2018-09-07 | 河南大学 | A kind of preparation method of carbon-supported metal tungsten nano particle |
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