CN104760940B - A kind of synthetic method of sandwich type composite nitride carbon - Google Patents
A kind of synthetic method of sandwich type composite nitride carbon Download PDFInfo
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- CN104760940B CN104760940B CN201510101503.2A CN201510101503A CN104760940B CN 104760940 B CN104760940 B CN 104760940B CN 201510101503 A CN201510101503 A CN 201510101503A CN 104760940 B CN104760940 B CN 104760940B
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Abstract
The present invention relates to the synthetic method of a kind of sandwich type carbonitride composite, belong to technical field of energy material.The carbonitride using different-shape prepares sandwich type composite, and this composite is applied to photocatalysis Isosorbide-5-Nitrae dihydropyridine aromatisation.Sandwich type carbonitride synthetic method is simple to operate, raw materials used cheap, and in whole building-up process, unharmful substance participates in and release, and investment of production is little.The application in photocatalysis Isosorbide-5-Nitrae dihydropyridine aromatisation of the described carbonitride composite, photocatalysis productivity is up to more than 99%.
Description
Technical field
The present invention relates to the synthetic method of a kind of sandwich type carbonitride composite, belong to technical field of energy material.
The carbon nitride precursor using different-shape prepares sandwich type composite, and this composite makees photosensitizer in photocatalysis field
There is broad prospect of application.
Background technology
Graphite phase carbon nitride is as the semi-conducting material of a kind of not metallic components, because of band structure and the excellence of its uniqueness
Chemical stability, by the extensive favor of scientists.With traditional TiO2Semi-conducting material is compared, the forbidden band width of carbonitride
Spend little, about 2.7eV (TiO2For 3.2eV), the solar spectrum medium wavelength royal purple light less than 475nm can be absorbed, nitrogenize simultaneously
Carbon also has most suitable quasiconductor bandedge placement, and it is led valence band value and lays respectively at-1.3V and+1.4V (vs NHE, pH=
7), it is widely used in photodissociation Aquatic product hydrogen and produces oxygen, the organic selectivity synthesis of photocatalysis, photocatalysis degradation organic contaminant etc..But,
Graphite phase carbon nitride also possesses conventional semiconductor material and has the shortcoming of some, and as little in specific surface area, photo-generate electron-hole is combined
Serious and quantum efficiency is low, and these defects seriously restrict its large-scale promotion application in photocatalysis field.By different band
The carbonitride of gap value is combined, and can effectively facilitate dissociating of exciton, accelerates light induced electron and the sharp separation in hole, suppression
Being combined of photo-generated carrier, regulates and controls its pattern, increases specific surface area, thus improves its photocatalysis efficiency.
Specific aim prepares new pattern carbonitride composite, selects graphite phase carbon nitride and mesoporous nitridation that band gap magnitude is different
Carbon, by the presoma of both physical mixed, prepares graphite-phase and mutually overlapping novel of mesoporous carbonitride after high-temperature calcination
Composite nitride carbon, i.e. class sandwich type composite nitride carbon, utilize its different-shape, increases specific surface area, regulates and controls band gap magnitude simultaneously.
And this sandwich type composite is applied to photocatalysis 1,4-dihydropyridine aromatisation.
Summary of the invention
It is an object of the present invention to provide the synthetic method of a kind of sandwich type carbonitride composite, by the nitrogen of different band gap magnitudes
After changing carbon matrix precursor physical mixed, high-temperature calcination is combined, and can be effectively improved the electron-hole separating power of material, increases ratio
Surface area, improves light-catalyzed reaction speed, and this NEW TYPE OF COMPOSITE carbonitride is applied to photocatalysis Isosorbide-5-Nitrae-dihydropyridine virtue first
Structure.
Concrete, the method for the synthesis nitridation carbon composite of the present invention comprises the following steps:
1. prepared by presoma
(1) being dissolved in the Ludox of 40% by cyanamide, be stirred overnight at a certain temperature, the transparent solid obtained fills
Divide and be ground to powder；
(2) weigh a certain amount of tripolycyanamide, be sufficiently mixed, before obtaining with the powder in step (1) according to different proportion
Drive body.
2. high-temperature calcination
The presoma obtained is put in crucible, calcines in Muffle furnace, be at the uniform velocity warming up to 400-800 DEG C, constant temperature one section
It is down to room temperature after time take out；
3. remove removing template
Use 4M NH4HF2Process 24h and remove removing template, centrifugal, washing, alcohol wash, dry after sandwich type composite nitride carbon.
4. photocatalysis 1,4-dihydropyridine aromatisation
By in the composite nitride carbon ultrasonic disperse of preparation to Isosorbide-5-Nitrae-dihydropyridine aqueous solution, stir under room temperature, at light source be
The xenon lamp of 30W reacts under irradiating, and light intensity is 100W/m2, reaction is every 10min sampling after starting, measure Isosorbide-5-Nitrae in solution-
Dihydropyridine changes at the absorbance of 350nm, and aromatization products changes at the absorbance of 280nm, calculates photocatalysis product
Productivity.
This synthetic method is simple to operate, raw materials used cheap, and in whole building-up process, unharmful substance participates in and releases
Putting, investment of production is little, and the carbonitride composite synthesized can be with efficient catalytic Isosorbide-5-Nitrae-dihydropyridine aromatisation.
Accompanying drawing explanation
Fig. 1 is example 1 in the present invention, example 2, example 3, comparative example 1, the infrared spectrogram of comparative example 2.
Fig. 2 is that TEM figure (a) SEM of sandwich type composite nitride carbon in example 2 in the present invention schemes (d).Stone in comparative example 1
TEM figure (b) of ink phase carbon nitride；TEM figure (c) of comparative example 2 intermediary hole carbonitride.
Fig. 3 is the photocatalysis 1,4-dihydropyridine suction of example 4 in the present invention, example 5, example 6, comparative example 3, comparative example 4
Shading value change (respectively scheming adceb) and 1,4-dihydropyridine conversion ratio variation diagram.
Detailed description of the invention
Embodiment 1
Taking in the Ludox that 5g cyanamide is dissolved in 12.5g 40%, under 333K, stirring in water bath is overnight.Obtain is transparent solid
Body is fully ground to powder, weighs after 0.83g tripolycyanamide is sufficiently mixed with powder and puts into crucible, calcines in Muffle furnace,
Heating rate is 2.3 DEG C/min, is warming up to 550 DEG C, is down to room temperature and takes out, use 4M NH after constant temperature 4h4HF2Process 24h and remove mould
Plate, centrifugal, washing, alcohol wash, dry after 25%-M-mpg-C3N4, specific surface area is 211.3m2/g。
Embodiment 2
Taking in the Ludox that 5g cyanamide is dissolved in 12.5g 40%, under 333K, stirring in water bath is overnight.Obtain is transparent solid
Body is fully ground to powder, weighs after 1.5g tripolycyanamide is sufficiently mixed with powder and puts into crucible, calcine in Muffle furnace, rises
Temperature speed is 2.3 DEG C/min, is warming up to 550 DEG C, is down to room temperature and takes out, use 4M NH after constant temperature 4h4HF2Process 24h and remove removing template,
Centrifugal, washing, alcohol wash, dry after 37.5%-M-mpg-C3N4, specific surface area is 231.3m2/g。
Embodiment 3
Taking in the Ludox that 5g cyanamide is dissolved in 12.5g 40%, under 333K, stirring in water bath is overnight.Obtain is transparent solid
Body is fully ground to powder, weighs after 2.5g tripolycyanamide is sufficiently mixed with powder and puts into crucible, calcine in Muffle furnace, rises
Temperature speed is 2.3 DEG C/min, is warming up to 550 DEG C, is down to room temperature and takes out, use 4M NH after constant temperature 4h4HF2Process 24h and remove removing template,
Centrifugal, washing, alcohol wash, dry after 50%-M-mpg-C3N4, specific surface area is 190.1m2/g。
Comparative example 1
Putting in crucible by 3g tripolycyanamide, calcine in Muffle furnace, heating rate is 2.3 DEG C/min, is warming up to
550 DEG C, constant temperature 4h is down to room temperature and takes out, and obtains graphite phase carbon nitride after washing and drying, and specific surface area is 16.9m2/g。
Comparative example 2
5g cyanamide is dissolved in the Ludox of 12.5g 40%, and under 333K, stirring in water bath is overnight.The transparent solid obtained
Putting into after being fully ground in crucible, calcine in Muffle furnace, heating rate is 2.3 DEG C/min, is warming up to 550 DEG C, constant temperature
4h is down to room temperature and takes out, and uses 4M NH4HF2Process 24h and remove template, centrifugal, washing, alcohol wash, dry after obtain mesoporous carbonitride,
Specific surface area is 157.3m2/g。
Embodiment 4
Take 20mg 25%-M-mpg-C3N4Ultrasonic disperse is to 10-3In M Isosorbide-5-Nitrae-dihydropyridine aqueous solution, stir under room temperature,
Reacting under the xenon lamp that light source is 30W irradiates, light intensity is 100W/m2, reaction is every 10min sampling after starting, and measures molten
In liquid, Isosorbide-5-Nitrae-dihydropyridine changes at the absorbance of 350nm, and aromatization products changes at the absorbance of 280nm, calculates light
The productivity of catalysis.Response time is 60min, and photocatalysis productivity is more than 99%.
Embodiment 5
Take 20mg 37.5%-M-mpg-C3N4Ultrasonic disperse is to 10-3In M Isosorbide-5-Nitrae-dihydropyridine aqueous solution, stir under room temperature
Mixing, react under the xenon lamp that light source is 30W irradiates, light intensity is 100W/m2, reaction is every 10min sampling after starting, and measures
In solution, Isosorbide-5-Nitrae-dihydropyridine changes at the absorbance of 350nm, and aromatization products changes at the absorbance of 280nm, calculates
Light-catalysed productivity.Response time is 40min, and photocatalysis productivity is more than 99%.
Embodiment 6
Take 20mg 50%-M-mpg-C3N4Ultrasonic disperse is to 10-3In M Isosorbide-5-Nitrae-dihydropyridine aqueous solution, stir under room temperature,
Reacting under the xenon lamp that light source is 30W irradiates, light intensity is 100W/m2, reaction is every 10min sampling after starting, and measures molten
In liquid, Isosorbide-5-Nitrae-dihydropyridine changes at the absorbance of 350nm, and aromatization products changes at the absorbance of 280nm, calculates light
The productivity of catalysis.Response time is 60min, and photocatalysis productivity is more than 99%.
Comparative example 3
Take 20mg graphite phase carbon nitride ultrasonic disperse to 10-3In M Isosorbide-5-Nitrae-dihydropyridine aqueous solution, stir under room temperature, at light
Source be 30W xenon lamp irradiate under react, light intensity is 100W/m2, reaction is every 10min sampling after starting, and measures in solution
Isosorbide-5-Nitrae-dihydropyridine changes at the absorbance of 350nm, and aromatization products changes at the absorbance of 280nm, calculates photocatalysis
Productivity.Response time is 160min, and photocatalysis productivity is 62.5%.
Comparative example 4
Take 20mg mesoporous carbonitride ultrasonic disperse to 10-3In M Isosorbide-5-Nitrae-dihydropyridine aqueous solution, stir under room temperature, at light source
For reacting under the xenon lamp irradiation of 30W, light intensity is 100W/m2, reaction is every 10min sampling after starting, and measures in solution 1,
4-dihydropyridine changes at the absorbance of 350nm, and aromatization products changes at the absorbance of 280nm, calculates light-catalysed
Productivity.Response time is 80min, and photocatalysis productivity is more than 99%.
Claims (3)
1. a preparation method for sandwich type composite nitride carbon, is applied to photocatalysis Isosorbide-5-Nitrae-dihydropyridine aromatisation, multiple
Closing carbonitride pattern is sandwich type, and after using the presoma mixing of graphite phase carbon nitride and mesoporous carbonitride, high-temperature process obtains
Arriving, the preparation method of this sandwich type composite nitride carbon comprises the following steps:
1. prepared by presoma
(1) being dissolved in the Ludox of 40% by cyanamide, under 298-400K, heated and stirred is overnight, and the transparent solid obtained is abundant
It is ground to powder；
(2) weigh a certain amount of tripolycyanamide, be sufficiently mixed with the powder in step (1) according to different proportion, obtain presoma；
2. high-temperature calcination
Putting in crucible by the presoma obtained, calcine in Muffle furnace, heating rate is 1-5 DEG C/min, is warming up to 400-600
DEG C, it is down to room temperature after constant temperature 4-6h and takes out；
3. removing template is removed
Use 4M NH4HF2Process 24h and remove removing template, centrifugal, washing, alcohol wash, dry after sandwich type composite nitride carbon.
2. according to the preparation method of claim 1 sandwich type composite nitride carbon, it is characterised in that: heated and stirred under 298-400K
Overnight, after the solid abrasive obtained, tripolycyanamide with 25%-50% is sufficiently mixed and prepares presoma.
3. according to the preparation method of sandwich type composite nitride carbon in claim 1, it is characterised in that: presoma calcination condition is
In course of reaction, programming rate controls, at 1-5 DEG C/min, to be warming up to 400-600 DEG C, is down to room temperature after constant temperature 4-6h.
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| CN105032465B (en) * | 2015-07-21 | 2017-06-06 | 北京化工大学 | Metal oxide/nitridation carbon composite and its preparation method and application |
| CN108325558B (en) * | 2018-02-11 | 2019-11-22 | 中国科学技术大学 | A kind of composite photo-catalyst and preparation method thereof and application |
| CN113023692B (en) * | 2021-03-25 | 2022-03-11 | 台州学院 | Preparation method of graphite-phase carbon nitride inverse opal structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20100128622A (en) * | 2009-05-28 | 2010-12-08 | 인하대학교 산학협력단 | Carbo-nitride mesopore |
| CN103145108A (en) * | 2013-02-07 | 2013-06-12 | 重庆工商大学 | Preparation method of C3N4 organic heterojunction |
| CN103818887A (en) * | 2014-03-26 | 2014-05-28 | 上海交通大学 | Method for preparing g-C3N4 photocatalysts with different shapes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20100128622A (en) * | 2009-05-28 | 2010-12-08 | 인하대학교 산학협력단 | Carbo-nitride mesopore |
| CN103145108A (en) * | 2013-02-07 | 2013-06-12 | 重庆工商大学 | Preparation method of C3N4 organic heterojunction |
| CN103818887A (en) * | 2014-03-26 | 2014-05-28 | 上海交通大学 | Method for preparing g-C3N4 photocatalysts with different shapes |
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