CN106881134A - The preparation of mesoporous carbon-nitrogen material and mesoporous carbon-nitrogen material and application - Google Patents
The preparation of mesoporous carbon-nitrogen material and mesoporous carbon-nitrogen material and application Download PDFInfo
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- CN106881134A CN106881134A CN201510943859.0A CN201510943859A CN106881134A CN 106881134 A CN106881134 A CN 106881134A CN 201510943859 A CN201510943859 A CN 201510943859A CN 106881134 A CN106881134 A CN 106881134A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a kind of preparation method of the mesoporous carbon-nitrogen material of bimetal-doped, hard template method is used to prepare mesoporous carbon-nitrogen material as catalyst precursor using containing n-donor ligand, carrying out bimetallic back loading with certain proportion afterwards is prepared.The catalysis material that the method synthesizes is applied to benzene hydroxylation reaction, the good stability of the material is presented in gentle reaction condition.
Description
Technical field
The present invention relates to the preparation method of the mesoporous carbon-nitrogen material of bimetal-doped, with containing n-donor ligand
It is dissolved in certain solvent as catalyst precursor, is afterwards dispersed in hard mould agent above-mentioned molten
In liquid, after being stirred vigorously certain hour, volatilize and high-temperature calcination under a nitrogen, hydrogen fluorine is used afterwards
Hard mould agent therein is washed so as to obtain mesoporous carbon-nitrogen material in acid off, afterwards by two kinds of source metals
It is prepared in this mesoporous carbon-nitrogen material with certain proportion back loading.
Background technology
Phenol is a kind of important chemical intermediate, can be used to produce bisphenol-A, phenolic resin,
Dyestuff, antioxidant and medicine etc..At present, phenol whole world demand is close to 1,000 ten thousand tons,
And the demand of China Pyrogentisinic Acid accounts for the 10% of world's aggregate demand.The traditional production method of phenol
It is cumene method, 95% phenol is produced by the method in the world at present.In the method, isopropyl
The hydrolysis of benzene needs substantial amounts of inorganic acid, brings certain environmental problem；Can be joined again simultaneously
The restriction in product acetone market.Especially in overall process, the phenol total recovery based on benzene feedstock
Only 5%.Therefore, no matter consider from the angle or Atom economy of sustainable development, people
Be intended to the method that is aoxidized by green catalysis always, the step of direct oxidation benzene one prepares phenol.
But, in benzene hydroxylation reaction, benzene feedstock is stable in properties, it is difficult to be oxidized, meanwhile, produce
Thing phenol property is active, and further oxidative degradation easily occurs, therefore, benzene direct oxidation is produced
Phenol is always a major challenge of field of catalytic chemistry, and especially the benzene with molecular oxygen as oxygen source is straight
It is considered as always one of great difficult problem of current catalytic field to connect and aoxidize the research of phenol processed.
With H2O2It is it is intended that substitution isopropyl to the direct liquid phase oxidation phenol of benzene for oxidant
Benzene method route produces another route of phenol.Use H2O2As oxidant, its unique accessory substance
It is H2O2Atom economy is high, and environment is not polluted, and is a kind of environment-friendly clean oxidation
Agent.Phenol is easier oxidation generation catechol, hydroquinones, benzoquinones and tar relative to benzene
Deng accessory substance, so as to cause to react low selectivity.After HTS comes out, the head such as Perego
It is secondary to use it for catalysis of phenol synthesis.Subsequent Thangaraj etc. reports H2O2As oxidant
Titanium molecular sieve catalysis Benzene to phenol.People are also attempted with VO2+ functionalization
(APTS)/MCM-41, LaMn-MCM-41, Co (V, Nb, La)-MCM-41and Fe/ live
Property charcoal obtains benzene conversion ratio 50-65% for catalyst, and H2O2Selectivity is only 17-50%.
But, existing benzene hydroxylation reaction system efficiency is very low.The present invention is by with mesoporous carbon-nitrogen material
For carrier more exposes chain carrier, strengthen catalyst mass transfer ability and bimetallic is lived
Property center concerted catalysis activation substrate benzene and H2O2, greatly improve benzene hydroxylation catalyst system and catalyzing
Activity.
Document is there is no at present in benzene hydroxylation field using the mesoporous carbon-nitrogen material of bimetal-doped
Report.
The content of the invention
The purpose of the present invention is a kind of bimetallic for being suitable for being catalyzed benzene hydroxylation phenol of exploitation
The preparation method of the mesoporous carbon-nitrogen material of doping.
The mesoporous carbon nitrogen material of the bimetal-doped of the catalysis benzene hydroxylation phenol that the present invention is provided
Material, is dissolved in certain solvent, afterwards by hard template using containing n-donor ligand as catalyst precursor
Agent is dispersed in above-mentioned solution, after being stirred vigorously certain hour, volatilizes and high temperature is forged under a nitrogen
Burn, afterwards washed so as to obtain mesoporous carbon-nitrogen material off hard mould agent therein with hydrofluoric acid, it
Two kinds of source metals are prepared with certain proportion back loading in this mesoporous carbon-nitrogen material afterwards.
It is suitable for containing n-donor ligand of the invention for pyridine, 2,2 '-bipyridyl, phenanthroline, bidppz
And the macrocyclic compound such as phthalein cyanogen.Wherein optimal is bidppz.
In the present invention, hard mould agent is Ludox (12nmSiO2), SBA-15, montmorillonite.It is excellent
Elect Ludox as.
In the present invention, containing n-donor ligand is 0.5-3 with the mass ratio of hard mould agent.Preferably 1.5.
In the present invention, nitrogenous catalyst and hard mould agent incorporation time are between 1~24h.
In the present invention, hydrofluoric acid consumption is to be added according to mass ratio with hard mould agent, quality
Than being 5:1~20:1, preferably 9:1~11:1.
In the present invention, calcining heat is preferably 800 DEG C for 500-1000 DEG C of under nitrogen.
In the present invention, the hydrofluoric acid wash hard mould agent time is preferably 24h. for 12~48h.
In the present invention, bimetallic presoma can be VO (acac) 2, TiCl4,
CrCl2,MnCl2,FeCl3,Co(oAc)2,Cu(OAc)2.
In the present invention, VO (acac) 2 is 1 with the mol ratio of another metal precursor：1~1：
10, preferably 1:3.
In the catalysis benzene hydroxylation reaction of this catalysis material, V and another metal in catalyst
Mole summation is 1 with benzene mol ratios:1000~1:50.
This catalysis material catalysis benzene hydroxylation reaction in, oxidant H2O2 with benzene moles
Than being 1:10~10:1.
In the catalysis benzene hydroxylation reaction of this catalysis material, it is oxidation that 30%~50%H2O2 can be used
Agent.
In the catalysis benzene hydroxylation reaction of this catalysis material, the catalysis benzene hydroxylation reaction of this catalysis material
Temperature is 25~80 degree.
Brief description of the drawings
Fig. 1：The ESEM collection of illustrative plates of the bimetallic catalyst of embodiment 1.
Specific embodiment
Specific implementation step of the invention is described in detail below by some embodiments, should not be by these realities
Example is applied to be limited as the scope of the invention.
Embodiment 1
270mgbidppz is taken in 40ml ethanol, is stirred vigorously to dissolving, add 1g silicon molten
Glue, is stirred vigorously 12h, volatilizes ethanol at 90 DEG C obtain yellow-brown solid afterwards, by it
2h is calcined at 800 DEG C under a nitrogen, obtains 650mg black powder solid catalysts.To
It adds 4g 40wt%HF acid and 4g water to be stirred vigorously 24h so as to by hard mould agent therein
Wash off, and fallen unnecessary pickling with a large amount of water, black powder is finally given after filtration drying and is consolidated
After body 200mg. by this black powder solid be dispersed in 0.1mmolVO (acac) 2 with
In the ethanol solution of 0.3mmolCu (OAc) 2, after stirring 12h at room temperature, filter and at 80 DEG C
Under be drying to obtain.
Reacted for benzene hydroxylation using the catalysis material for obtaining, by 80mg catalyst, 0.78g
Benzene (10mmol), 6.8mL acetonitriles, 3.4g 30%H2O2 add reaction in 25mL flasks,
Magnetic agitation, reaction temperature is 60 DEG C, keeps 2h, and it is 16.3% to obtain phenol yield.
Embodiment 2
270mg phenanthrolines are taken in 40ml ethanol, is stirred vigorously to dissolving, add 1g silicon
Colloidal sol, is stirred vigorously 12h, volatilizes ethanol at 90 DEG C obtain yellow-brown solid afterwards, will
It calcines 2h at 900 DEG C under a nitrogen, obtains 650mg black powder solid catalysts.
4g 40wt%HF acid and 4g water is added to be stirred vigorously 24h so as to by hard template therein to it
Agent is washed off, and is fallen unnecessary pickling with a large amount of water, and black powder is finally given after filtration drying
After solid 150mg. by this black powder solid be dispersed in 0.05mmolVO (acac) 2 with
In the ethanol solution of 0.3mmolTiCl4, after stirring 12h at room temperature, filter and at 80 DEG C
It is drying to obtain.
Reacted for benzene hydroxylation using the catalysis material for obtaining, by 80mg catalyst, 0.78g
Benzene (10mmol), 6.8mL acetonitriles, 3.4g 30%H2O2 add reaction in 25mL flasks,
Magnetic agitation, reaction temperature is 80 DEG C, keeps 2h, and it is 14.1% to obtain phenol yield.
Embodiment 3
270mgbidppz is taken in 40ml ethanol, is stirred vigorously to dissolving, added
0.4gSBA-15, is stirred vigorously 12h, afterwards volatilizes ethanol at 90 DEG C and obtains brown color and consolidate
Body, will calcine 2h at its under a nitrogen 700 DEG C, obtains 650mg black powder solids and urges
Agent.4g 40wt%HF acid and 4g water is added to be stirred vigorously 24h so that will be therein to it
Hard mould agent is washed off, and is fallen unnecessary pickling with a large amount of water, is finally given after filtration drying black
This black powder solid is dispersed in after color powder solid 150mg.
In the ethanol solution of 0.05mmolVO (acac) 2 and 0.2mmol CrCl2,12h is stirred at room temperature
Afterwards, filter and be drying to obtain at 80 DEG C.
Reacted for benzene hydroxylation using the catalysis material for obtaining, by 80mg catalyst, 0.78g
Benzene (10mmol), 6.8mL acetonitriles, 3.4g 30%H2O2 add reaction in 25mL flasks,
Magnetic agitation, reaction temperature is 40 DEG C, keeps 1h, and it is 11.0% to obtain phenol yield.
Embodiment 4-10
Similar to embodiment 1, being different from part is：Hard mould agent, containing n-donor ligand species
And consumption, two kinds of metal species and consumption, catalyst preparation temperature, react as follows after terminating
As a result (table one)：
Table one
Embodiment 11-15
Similar to embodiment 1, being different from part is：Using different amino silanes, amino
The mol ratio of the mol ratio of silane and ferrocene carboxaldehyde, ferrocene carboxaldehyde and NaBH3 (CN),
Reaction temperature obtains following result (table two)：
Table two
The catalysis material that the method synthesizes is applied to benzene hydroxylation reaction, in gentle reaction condition exhibition
The good stability of the material is showed.
Claims (10)
1. the preparation method of the mesoporous carbon-nitrogen material of bimetal-doped, it is characterised in that：It is dissolved in solvent as catalyst precursor using containing n-donor ligand, hard mould agent is dispersed in above-mentioned solution afterwards, after stirring, volatilize and high-temperature calcination under a nitrogen, hard mould agent therein is washed off so as to obtain mesoporous carbon-nitrogen material with hydrofluoric acid afterwards, two kinds of source metals are carried on into this mesoporous carbon-nitrogen material afterwards is prepared.
2. method according to claim 1, it is characterised in that：Containing n-donor ligand is pyridine, 2,2 '-bipyridyl, phenanthroline, 11,11 '-bis (dipyrido [3,2-a:2,3-c] phenazinyl) one or two or more kinds in the macrocyclic compound such as (bidppz) and phthalein cyanogen.
3. method according to claim 1, it is characterised in that：Hard mould agent is Ludox (12nmSiO2), SBA-15, one or two or more kinds in montmorillonite；Preferably Ludox.
4. the method according to claim 1,2 or 3, it is characterised in that：Containing n-donor ligand is 0.5-3 with the mass ratio of hard mould agent, and preferably 1.5 nitrogenous catalyst and hard mould agent stirring incorporation time are between 1~24h.
5. method according to claim 1, it is characterised in that：Hydrofluoric acid consumption is to be added according to mass ratio with hard mould agent, and mass ratio is 5:1~20:1, preferably 9:1~11:1；The hydrofluoric acid wash hard mould agent time is preferably 24h for 12~48h..
6. method according to claim 1, it is characterised in that：Calcining heat is 500-1000 DEG C under nitrogen；Preferably 800 DEG C.Calcination time is 1~48h.
7. method according to claim 1, it is characterised in that：Bimetallic presoma can be VO (acac)2With TiCl4,CrCl2,MnCl2,FeCl3,Co(oAc)2,Cu(OAc)2In one kind；VO(acac)2It is 1 with the mol ratio of another metal precursor：1~1：10, preferably 1:3.
8. the mesoporous carbon-nitrogen material that a kind of claim 1-7 either method is obtained.
9. the mesoporous carbon-nitrogen material described in a kind of claim 8 should have use, it is characterised in that：This catalysis material is used to be catalyzed in benzene hydroxylation reaction.
10. application according to claim 9, it is characterised in that：30%~50%H can be used2O2It is oxidant, oxidant H2O2It is 1 with benzene mol ratios:10~10:1；This catalysis material catalysis benzene hydroxylation reaction temperature is 25~80 degree.
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| CN110124718A (en) * | 2019-05-13 | 2019-08-16 | 浙江师范大学 | A kind of monatomic catalyst of vanadium base and preparation method thereof for benzene direct oxidation phenol |
| CN114308101A (en) * | 2021-12-22 | 2022-04-12 | 华南理工大学 | Michelidonite-assisted synthesized carbon nitride nanosheet photocatalyst and preparation method and application thereof |
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| CN114308101A (en) * | 2021-12-22 | 2022-04-12 | 华南理工大学 | Michelidonite-assisted synthesized carbon nitride nanosheet photocatalyst and preparation method and application thereof |
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Application publication date: 20170623 |