CN103191780A - Functionalized carbon nitride photocatalyst capable of performing catalytic oxidization on benzene to synthesize phenol - Google Patents
Functionalized carbon nitride photocatalyst capable of performing catalytic oxidization on benzene to synthesize phenol Download PDFInfo
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Abstract
The invention relates to a functionalized carbon nitride photocatalyst capable of performing catalytic oxidization on benzene to synthesize phenol, and a preparation method and applications of the functionalized carbon nitride photocatalyst, belonging to the technical fields of material preparation and organic photosynthesis. The chemical formula of the functionalized carbon nitride photocatalyst is Fc-Ch=N-C3N4. The preparation method comprises the steps of: firstly, performing heat condensation to carbon nitride precursor; and synthesizing the functionalized carbon nitride photocatalyst by adopting a solvent reflux method. The prepared photocatalyst has high specific surface area, and the phenol synthesis by efficient catalytic oxidization on benzene can be realized. The functionalized carbon nitride photocatalyst is simple in technique, low in cost, and high in yield, meets the practical production demand and has larger application potential.
Description
Technical field
The invention belongs to the technical field that material preparation and organic photosynthetic become, be specifically related to functionalization carbonitride photochemical catalyst of a kind of benzene catalytic oxidation synthesizing phenol and its preparation method and application.
Background technology
Phenol is a kind of important Organic Chemicals, mainly for the manufacture of phenolic resins, and bisphenol-A and caprolactam.Wherein producing phenolic resins is maximum purposes, and it is over half to account for phenol yield.In addition, phenol also is the raw material of a lot of medicine (as salicylic acid, aspirin and sulfa drug etc.), synthetic perfume, dyestuff (as Disperse Red 3B).Simultaneously, a considerable amount of phenol are arranged for the production of the halo phenols, and the dilute aqueous solution of phenol can directly be used as anticorrisive agent and disinfectant.
In recent years, world's phenol production ability and demand sustainable growth, phenol market supply and demand situation was very nervous in 2005, and the situation of global phenol strained market supply in 2006 begins to ease up.The U.S. is phenol production state the biggest in the world, following closely be Japan.The North America, West Europe, middle Eastern Europe and African production capacity all have surplus, and the Asia is in the situation that supply falls short of demand because overall development speed is higher than world's overall development speed.Recently, the fast development of China's automobile, telecommunications, building industry and metallurgical industry makes the increase in demand of phenol downstream product, the sharp increase of phenol demand.At present, China's phenol yield can not satisfy domestic actual production demand, and all need a large amount of imports every year, and import volume presents ever-increasing trend.Although constantly extend and plant modification, because the problem of technology own, existing apparatus production capacity is very limited, and phenol yield only was about 440,000 tons in 2005, yet nearly 730,000 tons of consumption figures have 290,000 tons of needs dependence imports approximately; Domestic market Pyrogentisinic Acid's total demand was about 850,000 tons in 2007, yet China's phenol production ability is produced 850,000 tons at most, presses device 90% utilization of capacity and calculates, and output is about 76.5 ten thousand tons, therefore, China still needs import some phenol could satisfy the downstream consumption demand.This shows that producing phenol has very high economic potential.
At present, industrial most phenol production is from three step isopropylbenzene processes, but there is many inevitable shortcomings: 1) produce line length, processing step is many, atom utilization is lower; 2) existence is met heat, is met sour, the chance dangerously explosive intermediate product of alkali (peroxy isopropyl benzene); 3) the accessory substance acetone of amount of substances such as generation and phenol is the deadly defect of this route, is subjected to the serious restriction of the acetone market demand; 4) the isopropylbenzene route need consume big energy and reclaim unreacted benzene and separation purification phenol.At this deficiency, photocatalysis oxidation technique since cost is low, reaction condition is gentle and can be efficiently directly the catalytic oxidation benzene into phenol etc. advantage become a kind of desirable organic photosynthetic and become technology.
In recent years, graphite phase carbon nitride (g-C
3N
4) enjoy the extensive concern of domestic and international scientists as the photochemical catalyst of the friendly type of a kind of nonmetal environment, it is at photolysis water hydrogen (Nat. Mater. 2009,8,76), light degradation organic pollution (Adv. Mater. 2009,21,1609) become aspects such as (J. Am. Chem. Soc. 2010,132,16299) to have a wide range of applications with organic photosynthetic.We are combined into mesoporous carbonitride (mpg-C recently
3N
4) can be by photoinduction catalytic oxidation benzene into phenol (J. Am. Chem. Soc. 2009,131,11658), and under optimization preparation technology's condition, the productive rate of its phenol reaches and is 11.9% to the maximum.But it also exists many shortcomings, for example Fe-g-C
3N
4/ SBA-15 activity and stability also need to improve.This may be because its active sites some wrapped up by catalyst, reduce the contact area of active sites and reactant, thereby reduced activity.And Fe-g-C
3N
4And the active force between the carrier S BA-15 is more weak, so its stability also waits to improve.Therefore, we are by arriving mpg-C to organic active species ferrocene formaldehyde (Fc-CHO) by the grafting of surface chemistry method
3N
4The surface, experiment showed, that the catalyst of the surface-functionalized modification of being synthesized has very high activity and advantages of higher stability at the catalytic oxidation benzene into phenol.
Summary of the invention
The object of the present invention is to provide functionalization carbonitride photochemical catalyst of a kind of benzene catalytic oxidation synthesizing phenol and its preparation method and application, the photochemical catalyst of the present invention's preparation has high-specific surface area, can realize benzene efficiently catalyzing and oxidizing synthesizing phenol.Technology of the present invention is simple, and cost is low, the productive rate height, and realistic production needs, and bigger application potential is arranged.
For achieving the above object, the present invention adopts following technical scheme:
A kind of chemical formula of functionalization carbonitride photochemical catalyst of benzene catalytic oxidation synthesizing phenol is Fc-CH=N-C
3N
4, specific area is 10-400 m
2/ g, amorphous substance can effectively separate photo-generated carrier.
A kind of method for preparing the functionalization carbonitride photochemical catalyst of aforesaid benzene catalytic oxidation synthesizing phenol based on the product of thermal polycondensation, makes by the solvent refluxing method and to have highly active functionalization carbonitride photochemical catalyst.May further comprise the steps:
(1) cyanamide is dissolved in the commodity Ludox and (contains 40wt.% 12 nm SiO
2) in, the mass ratio of cyanamide and commodity Ludox is 1:0～5, adds thermal agitation up to the water evaporate to dryness, the white solid that obtains is at N
2Under the protection, 500～700 ℃ of heat treatment 1～10h join NH with the powder after the heat treatment
4HF
2Stir in the solution after 2 days, filter, wash, dry, obtain yellow powder, namely mesoporous carbonitride is standby;
The mesoporous carbonitride high degree of dispersion that (2) will make is in absolute ethyl alcohol, and the ethanolic solution of ferrocene formaldehyde splashes in the above-mentioned solution lentamente by constant pressure funnel, subsequently at 40～100 ℃ of solvent refluxing reaction 0.5～48h; Naturally after the cooling, through absolute ethanol washing, centrifugal, oven dry, make functionalization carbonitride photochemical catalyst.
Remarkable advantage of the present invention is:
(1) the present invention is applied to organic photocatalysis field with the functionalization carbonitride first, has big specific area, and photo-generated carrier can effectively separate, and is a kind of novel photochemical catalyst.
(2) whole technical process of the present invention is simple and easy to control, and energy consumption is low, the productive rate height, and cost is low, and realistic production needs, and is conducive to large-scale popularization.
(3) functionalization carbonitride catalytic oxidation benzene into phenol efficiently has activity stability preferably simultaneously.Can carry out separating treatment easily in the light-catalyzed reaction system, the photochemical catalyst renewable is strong, and the recycling rate of waterused height has very high practical value and application prospect widely.
Description of drawings
Fig. 1 is the powder X-ray RD figure of the functionalization carbonitride photochemical catalyst of embodiment 3 gained.
Fig. 2 is the transmission electron microscope picture of the functionalization carbonitride photochemical catalyst of embodiment 3 gained.
Fig. 3 is the liquid chromatogram of the functionalization carbonitride photochemical catalyst catalytic oxidation benzene into phenol of embodiment 3 gained.
Fig. 4 is the activity stability figure of the functionalization carbonitride photochemical catalyst catalytic oxidation benzene into phenol of embodiment 3 gained.
The specific embodiment
Below be several embodiments of the present invention, further specify the present invention, but the present invention is not limited only to this.
Embodiment 1
It at first is the preparation of carbonitride presoma
Take by weighing the cyanamide of 5g commodity, be dissolved in 12.5g commodity Ludox and (contain 40% 12 nm SiO
2) in, it is dried that 100 ℃ of heating are stirred to, and resulting white sample in 500 ℃ of heat treatment 4h, is obtained yellow powder.Powder is joined 4M NH
4HF
2Stir 24h in the solution and remove template, filter, washing, ethanol is washed, and 80 ℃ of vacuum drying namely get the mesoporous carbonitride photochemical catalyst of yellow powder.
Next is the preparation of functionalization carbonitride
Take by weighing the mesoporous carbonitride high degree of dispersion of 1g in the absolute ethyl alcohol of 50ml, the 200ml ethanol solution of dissolving 1g ferrocene formaldehyde is splashed in the above-mentioned solution lentamente by constant pressure funnel, 60 ℃ add thermal agitation 24h then, resulting solid is repeatedly washed with ethanol, at 80 ℃ of vacuum dryings, namely get functionalization carbonitride photochemical catalyst at last.
Embodiment 2
It at first is the preparation of carbonitride presoma
Take by weighing the cyanamide of 5g commodity, be dissolved in 2.5g commodity Ludox and (contain 40% 12 nm SiO
2) in, it is dried that 100 ℃ of heating are stirred to, and resulting white sample in 600 ℃ of heat treatment 4h, is obtained yellow powder.Powder is joined 4M NH
4HF
2Stir 24h in the solution and remove template, filter, washing, ethanol is washed, and 80 ℃ of vacuum drying namely get the mesoporous carbonitride photochemical catalyst of yellow powder.
Next is the preparation of functionalization carbonitride
Take by weighing the mesoporous carbonitride high degree of dispersion of 1g in the absolute ethyl alcohol of 50ml, the 200ml ethanol solution of dissolving 1g ferrocene formaldehyde is splashed in the above-mentioned solution lentamente by constant pressure funnel, 60 ℃ add thermal agitation 12h then, resulting solid is repeatedly washed with ethanol, at 80 ℃ of vacuum dryings, namely get functionalization carbonitride photochemical catalyst at last.
Embodiment 3
It at first is the preparation of carbonitride presoma
Take by weighing the cyanamide of 5g commodity, be dissolved in 2.5g commodity Ludox and (contain 40% 12 nm SiO
2) in, it is dried that 100 ℃ of heating are stirred to, and resulting white sample in 700 ℃ of heat treatment 2h, is obtained yellow powder.Powder is joined 4M NH
4HF
2Stir 24h in the solution and remove template, filter, washing, ethanol is washed, and 80 ℃ of vacuum drying namely get the mesoporous carbonitride photochemical catalyst of yellow powder.
Next is the preparation of functionalization carbonitride
Take by weighing the mesoporous carbonitride high degree of dispersion of 1g in the absolute ethyl alcohol of 50ml, the 200ml ethanol solution of dissolving 1g ferrocene formaldehyde is splashed in the above-mentioned solution lentamente by constant pressure funnel, 100 ℃ add thermal agitation 48h then, resulting solid is repeatedly washed with ethanol, at 80 ℃ of vacuum dryings, namely get functionalization carbonitride photochemical catalyst at last.
Embodiment 4
It at first is the preparation of carbonitride presoma
Take by weighing the cyanamide of 5g commodity, be dissolved in 12.5g commodity Ludox and (contain 40% 12 nm SiO
2) in, it is dried that 100 ℃ of heating are stirred to, and resulting white sample in 500 ℃ of heat treatment 2h, is obtained yellow powder.Powder is joined 4M NH
4HF
2Stir 24h in the solution and remove template, filter, washing, ethanol is washed, and 80 ℃ of vacuum drying namely get the mesoporous carbonitride photochemical catalyst of yellow powder.
Next is the preparation of functionalization carbonitride
Take by weighing the mesoporous carbonitride high degree of dispersion of 1g in the absolute ethyl alcohol of 50ml, the 200ml ethanol solution of dissolving 1g ferrocene formaldehyde is splashed in the above-mentioned solution lentamente by constant pressure funnel, 100 ℃ add thermal agitation 24h then, resulting solid is repeatedly washed with ethanol, at 80 ℃ of vacuum dryings, namely get functionalization carbonitride photochemical catalyst at last.
Embodiment 5
It at first is the preparation of carbonitride presoma
Take by weighing the cyanamide of 5g commodity, be dissolved in 18.75g commodity Ludox and (contain 40% 12 nm SiO
2) in, it is dried that 100 ℃ of heating are stirred to, and resulting white sample in 600 ℃ of heat treatment 8h, is obtained yellow powder.Powder is joined 4M NH
4HF
2Stir 24h in the solution and remove template, filter, washing, ethanol is washed, and 80 ℃ of vacuum drying namely get the mesoporous carbonitride photochemical catalyst of yellow powder.
Next is the preparation of functionalization carbonitride
Take by weighing the mesoporous carbonitride high degree of dispersion of 1g in the absolute ethyl alcohol of 50ml, the 200ml ethanol solution of dissolving 1g ferrocene formaldehyde is splashed in the above-mentioned solution lentamente by constant pressure funnel, 80 ℃ add thermal agitation 12h then, resulting solid is repeatedly washed with ethanol, at 80 ℃ of vacuum dryings, namely get functionalization carbonitride photochemical catalyst at last.
Embodiment 6
It at first is the preparation of carbonitride presoma
Take by weighing the cyanamide of 5g commodity, be dissolved in 18.75g commodity Ludox and (contain 40% 12 nm SiO
2) in, it is dried that 100 ℃ of heating are stirred to, and resulting white sample in 700 ℃ of heat treatment 8h, is obtained yellow powder.Powder is joined 4M NH
4HF
2Stir 24h in the solution and remove template, filter, washing, ethanol is washed, and 80 ℃ of vacuum drying namely get the mesoporous carbonitride photochemical catalyst of yellow powder.
Next is the preparation of functionalization carbonitride
Take by weighing the mesoporous carbonitride high degree of dispersion of 1g in the absolute ethyl alcohol of 50ml, the 200ml ethanol solution of dissolving 1g ferrocene formaldehyde is splashed in the above-mentioned solution lentamente by constant pressure funnel, 80 ℃ add thermal agitation 48h then, resulting solid is repeatedly washed with ethanol, at 80 ℃ of vacuum dryings, namely get functionalization carbonitride photochemical catalyst at last.
Performance test
Fig. 1 is the powder X-ray RD figure of the functionalization carbonitride of embodiment 3 gained.Can find that from figure prepared functionalization carbonitride is amorphous.Fig. 2 is the transmission electron microscope picture of the functionalization carbonitride of embodiment 3 gained.Can find that from figure the functionalization carbonitride for preparing is mesoporous pattern.Table 1 is that the functionalization carbonitride of embodiment 3 gained and the effect of commodity titanium dioxide P25 photochemical catalytic oxidation benzene into phenol compare.
The effect of table 1 functionalization carbonitride and commodity titanium dioxide P25 photochemical catalytic oxidation benzene into phenol relatively
Reaction by catalytic oxidation benzene into phenol under radiation of visible light is tested the activity of functionalization carbonitride photochemical catalyst.Closed reactor is adopted in reaction, and liquid benzene is dissolved in (benzene concentration is about 0.968mmol/ml) in the acetonitrile-water mixed solution, and catalyst consumption is 0.05 g, 60 ℃ of constant temperature water baths.With xenon lamp (300 W,〉420nm) as light source, illumination reaction 4h stops reaction, after ice-water bath is cooled to 4 ℃, in reaction system, add ethanol and toluene, dilution, centrifugal, use high performance liquid chromatography (HPLC2487, C18) to detect the amount that phenol produces at last.As can be seen, behind the illumination 4h, the functionalization carbonitride can the catalytic oxidation benzene into phenol from table 1a, and its phenol yield reaches 16.5%(and selectively reaches 34.6% based on hydrogen peroxide).Comparing commodity photochemical catalyst P25 changing effect significantly improves.From table 1b as can be seen prepared catalyst take turns to second first and take turns some reduction of reactivity, this may be that the active specy that is adsorbed onto mesoporous carbonitride because a part does not have grafting splits away off after first round reaction, but take turns to the fourth round course of reaction from second, catalyst has kept higher activity.So prepared catalyst still has higher activity stability.
Fig. 3 is the liquid chromatogram of the functionalization carbonitride photochemical catalyst catalytic oxidation benzene into phenol of embodiment 3 gained.As can be seen from the figure prepared functionalization carbonitride photochemical catalyst mainly produces phenol (principal product) and a spot of other accessory substance in the photochemical catalytic oxidation benzene into phenol.The catalyst that this explanation is synthesized has very high activity and selective.
Fig. 4 is the activity stability figure of the functionalization carbonitride photochemical catalyst catalytic oxidation benzene into phenol of embodiment 3 gained.As can be seen from the figure prepared catalyst takes turns to second first and takes turns some reduction of reactivity, this may be that the active specy that is adsorbed onto mesoporous carbonitride because a part does not have grafting splits away off after first round reaction, but take turns to the fourth round course of reaction from second, catalyst has kept higher activity.So prepared catalyst still has higher activity stability.
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. the functionalization carbonitride photochemical catalyst of a benzene catalytic oxidation synthesizing phenol, it is characterized in that: the chemical formula of functionalization carbonitride photochemical catalyst is Fc-CH=N-C
3N
4
2. the functionalization carbonitride photochemical catalyst of benzene catalytic oxidation synthesizing phenol according to claim 1, it is characterized in that: the specific area of functionalization carbonitride photochemical catalyst is 10-400 m
2/ g, amorphous substance can effectively separate photo-generated carrier.
3. method for preparing the functionalization carbonitride photochemical catalyst of benzene catalytic oxidation synthesizing phenol as claimed in claim 1 is characterized in that: based on the product of thermal polycondensation, make by the solvent refluxing method and to have highly active functionalization carbonitride photochemical catalyst.
4. the preparation method of the functionalization carbonitride photochemical catalyst of benzene catalytic oxidation synthesizing phenol according to claim 3 is characterized in that: may further comprise the steps:
(1) cyanamide is dissolved in the commodity Ludox, the mass ratio of cyanamide and commodity Ludox is 1:0～5, adds thermal agitation up to the water evaporate to dryness, and the white solid that obtains is at N
2Under the protection, 500～700 ℃ of heat treatment 1～10h join NH with the powder after the heat treatment
4HF
2Stir in the solution after 2 days, filter, wash, dry, obtain yellow powder, namely mesoporous carbonitride is standby;
The mesoporous carbonitride high degree of dispersion that (2) will make is in absolute ethyl alcohol, and the ethanolic solution of ferrocene formaldehyde splashes in the above-mentioned solution lentamente by constant pressure funnel, subsequently at 40～100 ℃ of solvent refluxing reaction 0.5～48h; Naturally after the cooling, through absolute ethanol washing, centrifugal, oven dry, make functionalization carbonitride photochemical catalyst.
5. the application of the functionalization carbonitride photochemical catalyst of a benzene catalytic oxidation synthesizing phenol as claimed in claim 1 is characterized in that: described functionalization carbonitride photochemical catalyst is used for benzene efficiently catalyzing and oxidizing synthesizing phenol.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623856A (en) * | 2013-12-10 | 2014-03-12 | 福州大学 | Spherical mesoporous carbon nitride photocatalyst with multistage nano structure |
| CN106881134A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | The preparation of mesoporous carbon-nitrogen material and mesoporous carbon-nitrogen material and application |
| CN107262129A (en) * | 2017-06-13 | 2017-10-20 | 北京化工大学 | Light compositing hydrogen peroxide carbon nitrogen catalyst and preparation method thereof |
| CN107488133A (en) * | 2017-08-18 | 2017-12-19 | 福州大学 | A kind of method of carbonitride photocatalysis synthesis of carbamates class compound |
| CN107511160A (en) * | 2017-08-07 | 2017-12-26 | 锡林郭勒职业学院 | A kind of MOX/g C3N4@SiO2The preparation method and applications of catalyst |
| CN112023971A (en) * | 2020-08-26 | 2020-12-04 | 中国科学院山西煤炭化学研究所 | Application of cyano-modified carbon nitride in phenol photo-mineralization field |
| CN115337947A (en) * | 2022-07-19 | 2022-11-15 | 浙江大学 | Metal atom high-doping-amount monatomic catalyst, preparation method and application thereof |
| CN115364902A (en) * | 2022-07-19 | 2022-11-22 | 浙江大学 | Preparation of high-efficiency photocatalyst and application of high-efficiency photocatalyst in sewage treatment |
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| CN103623856B (en) * | 2013-12-10 | 2015-04-15 | 福州大学 | Spherical mesoporous carbon nitride photocatalyst with multistage nano structure |
| CN103623856A (en) * | 2013-12-10 | 2014-03-12 | 福州大学 | Spherical mesoporous carbon nitride photocatalyst with multistage nano structure |
| CN106881134A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | The preparation of mesoporous carbon-nitrogen material and mesoporous carbon-nitrogen material and application |
| CN107262129B (en) * | 2017-06-13 | 2019-08-13 | 北京化工大学 | Photosynthesis hydrogen peroxide carbon nitrogen catalyst and preparation method thereof |
| CN107262129A (en) * | 2017-06-13 | 2017-10-20 | 北京化工大学 | Light compositing hydrogen peroxide carbon nitrogen catalyst and preparation method thereof |
| CN107511160B (en) * | 2017-08-07 | 2020-06-23 | 锡林郭勒职业学院 | MOX/g-C3N4@SiO2Preparation method and application of catalyst |
| CN107511160A (en) * | 2017-08-07 | 2017-12-26 | 锡林郭勒职业学院 | A kind of MOX/g C3N4@SiO2The preparation method and applications of catalyst |
| CN107488133B (en) * | 2017-08-18 | 2019-08-09 | 福州大学 | A kind of method of carbonitride photocatalysis synthesis of carbamates class compound |
| CN107488133A (en) * | 2017-08-18 | 2017-12-19 | 福州大学 | A kind of method of carbonitride photocatalysis synthesis of carbamates class compound |
| CN112023971A (en) * | 2020-08-26 | 2020-12-04 | 中国科学院山西煤炭化学研究所 | Application of cyano-modified carbon nitride in phenol photo-mineralization field |
| CN115337947A (en) * | 2022-07-19 | 2022-11-15 | 浙江大学 | Metal atom high-doping-amount monatomic catalyst, preparation method and application thereof |
| CN115364902A (en) * | 2022-07-19 | 2022-11-22 | 浙江大学 | Preparation of high-efficiency photocatalyst and application of high-efficiency photocatalyst in sewage treatment |
| CN115364902B (en) * | 2022-07-19 | 2024-04-05 | 浙江大学 | Preparation of high-efficiency photocatalyst and application of high-efficiency photocatalyst in sewage treatment |
| CN115337947B (en) * | 2022-07-19 | 2024-04-05 | 浙江大学 | Metal atom high-doping-amount monoatomic catalyst, preparation method and application thereof |
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