CN105689012B - A kind of preparation method of Nano diamond solid acid catalyst - Google Patents
A kind of preparation method of Nano diamond solid acid catalyst Download PDFInfo
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- CN105689012B CN105689012B CN201610179483.5A CN201610179483A CN105689012B CN 105689012 B CN105689012 B CN 105689012B CN 201610179483 A CN201610179483 A CN 201610179483A CN 105689012 B CN105689012 B CN 105689012B
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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Abstract
A kind of preparation method of Nano diamond solid acid catalyst, is comprised the following steps that：N-terminal modification is carried out to Nano diamond powder using radio frequency plasma radio-frequency technique.Then, it is assist medium from zirconium particle is changed, stable dispersions of the Nano diamond in tetrahydrofuran or solvent dimethylformamide is obtained using ultrasonic disperse technology.Finally, using the N-terminal on Nano diamond surface and 1, the reaction of 3 sultone, sulfonic acid acid point is prepared in Nano diamond, using deionized water eccentric cleaning and drying, obtains Nano diamond solid acid catalyst final product.The present invention is based on the modification of Nano diamond particle surface N-terminal and sulfonating reaction, it is proposed that a kind of novel nano diamond solid acid catalyst preparation method.With it is existing be based on hydroxy terminal Nano diamond preparation method compared with, outstanding advantages of there is preparation method of the present invention the reaction time significantly to shorten, and technological process is simple and easy.
Description
Technical field
The invention belongs to nano-functional material field, specially a kind of preparation side of Nano diamond solid acid catalyst
Method.
Background technology
Solid acid catalyst is a kind of important catalyst.Its catalysis has from present on solid material surface
The acid sites of catalytic activity, claim acid site.This kind of catalyst is widely used in alkaline sewage processing, ester type compound synthesizes,
The fields such as fuel cell ion conductor.Compared with conventional liquid acid, solid acid has acid strength height, corrosivity in catalyst system and catalyzing
It is low and outstanding advantages of be easily isolated.Solid acid catalysis agent material is mostly non-transition element oxide and simple substance carbon particle at present.
Wherein, nano material is big compared with high specific surface area because of having, and hydrophobicity is strong, adsorbs the features such as compatibility is good with organic matter,
It is considered as the desired matrix material of solid acid catalyst.However, under some particular service requirements, common nano-powder due to
Its high surface energy causes its chemical stability poor, makes it be not appropriate for using as the matrix material of solid acid catalyst.
For example, when manufacturing the ion conductor in fuel cell, solid acid catalyst used is needed under hot conditions, keeps chi for a long time
Very little stabilization and surface acidity, to ensure the service life of fuel cell.On this condition, traditional nano-oxide solid acid
Catalyst is extremely difficult to requirement, and Nano diamond solid catalyst is then because it has thermostabilization, high mechanical strength and change
Learn the ideal chose that the stable advantage of property is considered as this kind of solid catalyst matrix.
Because diamond itself chemical stability is higher, thus acid site is obtained on its surface, it is necessary to it is entered first
Row chemical modification.The Nano diamond solid acid catalyst preparation method reported at present only has one kind.Concretely comprise the following steps：It is first
First, the Nano diamond for having oh group to surface modification using hydrogen peroxide carries out purification process, then in turn through deionization
Water, isopropanol and acetone cleaning, are redispersed in 1,3- in sulphur ester/toluene system, and 100 DEG C of stirring reaction certain times are (generally
For 24h) obtain the solid acid catalyst that there is sulfonic acid acid to select on surface.From the point of view of practical application effect, above-mentioned preparation method is main
In the presence of two subject matters, first, because the surface energy of Nano diamond is high, long-time pyroreaction easily causes nano particle
Reunite, follow-up twice dispersing is more difficult, so as to influence catalytic activity.Second, above method reaction time length, temperature
Height, need in course of reaction to set the condensation reflux unit of toluene, equipment is complicated, and power consumption is high, is unfavorable for large-scale production.For
This, the present invention proposes a kind of novel nano diamond solid acid catalyst preparation method based on ultrasonic disperse technology.
The content of the invention
The application utilizes zirconium dioxide assisting ultrasonic dispersion technology, overcomes existing Nano diamond solid acid catalyst to prepare
Agglomeration traits in technology.Compared with conventional method, the shortening in reaction time and the reduction of temperature are also to overcoming reunion helpful
Effect, the large-scale production of such catalyst is realized, the application utilizes the Nano diamond with N-terminal, auxiliary in ultrasonic wave
A kind of novel nano diamond solid acid catalyst is quickly prepared under the conditions of helping.Compared with the conventional method, this method has anti-
It is short between seasonable, outstanding advantages of nano particle is not easy to reunite.
To achieve these goals, the technical scheme that the application is taken is as follows：
A kind of Nano diamond solid acid catalyst, its structural formula are as follows：
When the catalyst is in alkaline environment, with the H in catalyst molecule structure, combined with acid site+Will be with causing dirt
Ion-exchange reactions occurs for the metal cation for raping salt of weak acid of dye so that the pH value in solution reduces, and Nano diamond exists
Lose colloidal stability in solution dispersion system and reunite and settle.Now, by precipitum secondary recovery and weight can be subject to
It is multiple to utilize, solve the problems, such as that traditional liquid acid can not separate.
Nano diamond solid acid catalyst processes are prepared, are comprised the following steps that：
(1) N-terminal modification is carried out to Nano diamond powder；
(2) the Nano diamond powder by N-terminal modification obtained by step (1) is purified and disperseed；
(3) product of the step (2) after treated is subjected to sulfonation processing, produces Nano diamond solid acid catalyst.
Described, in step (1), N-terminal modification is carried out to Nano diamond powder and comprised the following steps that：
Deionized water, ammoniacal liquor, EtOH Sonicate are carried out respectively successively to nanometer monocrystalline diamond of the particle mean size less than 100nm
Cleaning 10 minutes, then be placed in the vacuum chamber of low pressure plasma processing equipment, it is evacuated to below 10Pa；According still further to stream
Measure ratio 2：1 is passed through hydrogen and nitrogen simultaneously, finally applies radio frequency electrical to vacuum indoor gas, obtains plasma, handles 5-20
Sample is taken out after minute, that is, obtaining surface modification has the Nano diamond powder of N-terminal, abbreviation ND.
Described plasma discharge power is 100w；
In the presence of high-frequency electrical, nitrogen and hydrogen are ionized to the powered nitrogen and hydrogen ion of activity, while ND surfaces
C h bond is opened, so as to form C-NH on ND surfaces again2Structure.
The specific step that the Nano diamond powder modified by N-terminal is purified and disperseed in described step (2)
It is rapid as follows：
100-200 times according to ND weight weighs zirconium dioxide powder (ZrO2), by ZrO2Container bottom is placed in, thereon
After even paving spills ND, then enough addition tetrahydrofurans (THF) or dimethylformamide (DMF), container is placed in processor for ultrasonic wave
Middle processing 2 hours, centrifugal treating, removes ZrO2, obtain ND dispersion liquids；
Described tetrahydrofuran (THF) or dimethylformamide (DMF) dosage are 5-10 times of all solids volume.
The Nano diamond of powder is the head existing for Nano diamond aggregate, to become nano particle again
First seek to act on by ultrasonic oscillation, it is scatter in the THF or DMF solvent with high polarity；In this process
Middle ZrO2Diamond particle surfaces can be constantly hit, play a part of removing ND crystal defects and impurity.
Described sulfonation processing, is comprised the following steps that：1, the 3- sultone of 2 times of ND weight is added in ND dispersion liquids
(PS) after, being ultrasonically treated 6-8 hours at room temperature, using deionized water eccentric cleaning three times after, sediment through dry obtain it is final
Product.The reaction principle is as shown in Figure 1.
With it is existing be based on hydroxy terminal Nano diamond preparation method compared with, preparation method of the present invention have reaction
Outstanding advantages of time significantly shortens, and technological process is simple and easy.Specially：1.ZrO2The scattered introducing of particle assisting ultrasonic with
And whole course of reaction is carried out under Ultrasonic Conditions, effectively prevent nanoparticle agglomerates；2. maximum difference is to be based on ammonia
Base terminal connects sulfonic acid.Before with hydroxy terminal, in the case where toluene evaporates counterflow condition, react more than 24 hours, equipment work
Skill is complicated, and more than 110 degrees Celsius secondary agglomeration easily occurs for temperature.And the reaction time of the invention is 6-8 hours, and effect
Well.
ND is the abbreviation for the Nano diamond powder that surface modification has N-terminal；
Brief description of the drawings
Fig. 1 is the Nano diamond sulfonating reaction schematic diagram for being modified with N-terminal；
Fig. 2 is ND diamonds solid acid catalyst FTIR spectral lines described in embodiment 2.
Embodiment
Embodiment 1
A kind of preparation method of Nano diamond solid acid catalyst, is comprised the following steps that：
(1) N-terminal modification is carried out to Nano diamond powder.Select average grain diameter 20-30nm nanometer monocrystalline Buddha's warrior attendant
Stone carries out deionized water, ammoniacal liquor, EtOH Sonicate and cleans 10 minutes, then be placed on the true of low pressure plasma processing equipment successively
In empty room, 2Pa is evacuated to.Then, while with 0.5L/min and 1L/min flow hydrogen and nitrogen are passed through into vacuum chamber
(purity is 99.99%).Finally, frequency 10MHz square wave is applied between electrode and vacuum chamber housing in vacuum chamber
Radio frequency electrical, obtain plasma.After plasma glow is stable, stablizes 15 minutes, close radio-frequency power supply and gas successively, beat
Vacuum chamber is opened, takes out ND.
(2) purifying of Nano diamond is with disperseing.Weigh ND200mg, average grain diameter 0.05mm ZrO240g, by ZrO2Put
In container bottom, uniformly paving spills ND thereon, adds 20mLTHF.Then, the container for holding above-mentioned sample is placed in ice bath,
The ultrasonic variable amplitude bar of processor for ultrasonic wave is inserted into container bottom, selects continuous and pulse plasma modelses, 20KHz frequency processings 2 hours.
Finally, 5000rpm centrifuges 5min, retains last time clear liquid, lower floor ZrO2Sediment through a small amount of THF eccentric cleanings twice, clear liquid with
It is ND dispersion liquids that centrifugation first, which obtains clear liquid to merge,.
(3) Nano diamond sulfonation is handled.400mgPS is added in ND dispersion liquids, (condition is same as above supersound process at room temperature
One step) after 6 hours, using deionized water eccentric cleaning three times after, sediment obtains final product through drying.
(4) FTIR testing results show C=C ,-OH and-SO in sample be present3The characteristic absorption peak of the functional groups such as H, says
Bright sulfonation is handled successfully.It is 83.2 ± 0.5nm using particle mean size of the laser particle analyzer measure product in water, Zeta potential
30.3mV。
Embodiment 2
A kind of preparation method of Nano diamond solid acid catalyst, is comprised the following steps that：
(1) N-terminal modification is carried out to Nano diamond powder.To particle mean size 60-80nm nanometer monocrystalline diamond
Deionized water, ammoniacal liquor, EtOH Sonicate is carried out successively to clean 10 minutes, then be placed on the vacuum of low pressure plasma processing equipment
In room, 1Pa is evacuated to.Then, while with 1L/min and 2L/min flow hydrogen and nitrogen (purity are passed through into vacuum chamber
It is 99.99%).Finally, frequency 15MHz square wave radio frequency is applied between electrode and vacuum chamber housing in vacuum chamber
Electricity, obtain plasma.After plasma glow is stable, stablizes 9 minutes, close radio-frequency power supply and gas successively, open true
Empty room, take out ND.
(2) purifying of Nano diamond is with disperseing.Weigh ND200mg, average grain diameter 0.05mm ZrO240g, by ZrO2Put
In container bottom, uniformly paving spills ND thereon, adds 30mLDMF.Then, the container for holding above-mentioned sample is placed in ice bath,
The ultrasonic variable amplitude bar of processor for ultrasonic wave is inserted into container bottom, selects continuous and pulse plasma modelses, 20KHz frequency processings 2 hours.
Finally, 5000rpm centrifuges 5min, retains last time clear liquid, lower floor ZrO2Sediment through a small amount of THF eccentric cleanings twice, clear liquid with
It is ND dispersion liquids that centrifugation first, which obtains clear liquid to merge,.
(3) Nano diamond sulfonation is handled.400mgPS is added in ND dispersion liquids, (condition is same as above supersound process at room temperature
One step) after 8 hours, using deionized water eccentric cleaning three times after, sediment obtains final product through drying.
(4) FTIR testing results show C=O ,-OH and-SO in sample be present3The characteristic absorption peak of the functional groups such as H, says
Bright sulfonation is handled successfully (as shown in Figure 2).It is 161.0 ± 0.5nm using granularity of the laser particle analyzer measure product in water,
Zeta potential 33.2mV.
Experimental example
If the water pollutant processing that the catalyst is used under alkaline environment, it must have good group under alkaline environment
Pollutant ability drops in coagulation.Therefore, its granularity and Zeta potential in PBS balanced salt solutions (pH=8.8) is further determined,
As a result it is as shown in table 1.It can be seen that after now aqueous systems add this solid acid catalyst, wherein average grain thing granularity be 1639 ±
0.4nm, Zeta potential is by rotating forward negative (- 17.4mV).Illustrate to reunite sedimentation substantially.
Granularity and Zeta potential change of the table 1ND solid acids in different medium
| Medium | Particle mean size/nm | Zeta potential/mV |
| Deionized water (embodiment 1) | 83.2±0.5 | 30.3 |
| PBS balanced salt solutions (embodiment 1) | 1437±0.3 | -18.2 |
| Deionization (embodiment 2) | 161.0±0.5 | 33.2 |
| PBS balanced salt solutions (embodiment 2) | 1639±0.4 | -17.4 |
Claims (6)
1. a kind of Nano diamond solid acid catalyst, it is characterised in that its structural formula is as follows：
2. prepare the method for Nano diamond solid acid catalyst as claimed in claim 1, it is characterised in that specific steps are such as
Under：
(1) N-terminal modification is carried out to Nano diamond powder；
(2) the Nano diamond powder by N-terminal modification obtained by step (1) is purified and disperseed；
(3) product of the step (2) after treated is subjected to sulfonation processing, produces Nano diamond solid acid catalyst.
3. the method as claimed in claim 2 for preparing Nano diamond solid acid catalyst, it is characterised in that described, step
Suddenly in (1), N-terminal modification is carried out to Nano diamond powder and comprised the following steps that：
Carry out deionized water, ammoniacal liquor, EtOH Sonicate cleaning respectively successively to nanometer monocrystalline diamond of the particle mean size less than 100nm
10 minutes, then be placed in the vacuum chamber of low pressure plasma processing equipment, it is evacuated to below 10Pa；According still further to flow-rate ratio
2：1, while hydrogen and nitrogen are passed through, radio frequency electrical is applied to vacuum indoor gas, obtains plasma, is taken after handling 5-20 minutes
Go out sample, that is, obtaining surface modification has the Nano diamond powder of N-terminal.
4. the method as claimed in claim 2 for preparing Nano diamond solid acid catalyst, it is characterised in that described, institute
The Nano diamond powder modified by N-terminal is purified in the step of stating (2) and that disperses comprises the following steps that：
100-200 times according to the nano-diamond powder body weight modified by N-terminal weighs zirconium dioxide powder, by ZrO2Put
In container bottom, uniformly paving spills the Nano diamond powder modified by N-terminal thereon, adds tetrahydrofuran or dimethyl
After formamide, container is placed in processor for ultrasonic wave and handled 2 hours, centrifugal treating, remove ZrO2, obtain and repaiied by N-terminal
The Nano diamond powder dispersion of decorations.
5. the method as claimed in claim 4 for preparing Nano diamond solid acid catalyst, it is characterised in that described tetrahydrochysene
Furans or dimethylformamide dosage are 5-10 times of all solids volume.
6. the method as claimed in claim 2 for preparing Nano diamond solid acid catalyst, it is characterised in that described sulfonation
Processing, is comprised the following steps that：Add in the Nano diamond powder dispersion modified by N-terminal and modified by N-terminal
2 times of nano-diamond powder body weight 1,3- sultone, at room temperature be ultrasonically treated 6-8 hours after, centrifuged using deionized water
After cleaning three times, sediment obtains final product through drying.
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| JPH07500876A (en) * | 1991-11-05 | 1995-01-26 | リサーチ・トライアングル・インスティテュート | Chemical vapor deposition of diamond films using water-based plasma discharge |
| US9079295B2 (en) * | 2010-04-14 | 2015-07-14 | Baker Hughes Incorporated | Diamond particle mixture |
| CN104047019A (en) * | 2013-03-11 | 2014-09-17 | 同济大学 | Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof |
| CN104646057A (en) * | 2013-11-19 | 2015-05-27 | 中国科学院金属研究所 | Polyacid/nano-carbon-hybridized solid acid catalyst, preparation method and application thereof |
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