CN109704301A - A kind of cobalt sulphur codope mesoporous carbon and its preparation method and application - Google Patents
A kind of cobalt sulphur codope mesoporous carbon and its preparation method and application Download PDFInfo
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Abstract
It is easy to spread by the way that using Citric Acid Mono, magnesium nitrate hexahydrate and cobalt salt as raw material, preparation method is simple, and manufacturing cost is low the invention discloses a kind of cobalt sulphur codope mesoporous carbon and its preparation method and application, it can be manufactured on a large scale；The cobalt sulphur codope mesoporous carbon product stability prepared simultaneously is high, and using it can be used to prepare aromatic amine compounds；When preparing aromatic amine compounds, react easily operated, in normal pressure, temperature can be carried out sound response under the conditions of being 50-70 DEG C, reaction condition compared to the prior art in generation method be easier to realize；The applicability of the cobalt sulphur codope meso-porous carbon material is wide simultaneously, can all play good catalytic effect to a variety of nitro compounds, substantially reduce the reaction time, maximum output can achieve 98%, general preparation method in compared to the prior art, yield are significantly increased, and economic benefit is higher.
Description
Technical field
The present invention relates to catalyst to synthesize field, more particularly to a kind of cobalt sulphur codope mesoporous carbon and its preparation
Methods and applications.
Background technique
Aromatic amine compounds are industrial important source materials, and purposes is very extensive, can be used for dyestuff, medicine, agricultural
The production of chemicals, additive, surfactant, textile auxiliary, chelating agent and polymer, fire retardant etc..
In the prior art, aromatic amine mainly is prepared by restoring the method for nitro, restoring method mainly has following several
Kind: 1. metals are in acid, neutral, alkaline system reduction method；2 chemical reduction methods: including sodium sulfide reducing method, NaBH4, hydration
Hydrazine reduction method etc.；3. catalytic hydrogenating reduction method.It is the reduction reaction of raw material additionally by the cheap nitrobenzene of from a wealth of sources, price
Also compare more to prepare the document of aniline, but this method usually requires a large amount of transition metal, also can in whole preparation process
Generate a large amount of inorganic wastes.2005, Second Military Medical University, PLA (CN1699351 [P] .2005-11-23)
It is realized under the catalysis of active nickel by research, under the reduction of hydrazine hydrate, by the process of reduction, realizes three nitrogen mile alcohol
The synthesis of class antifungal compound；2012, and Pralay Das et al. (Tetrahedron Lett, 2012,53:4858-
4861.) solid-state self-supporting zeroth order palladium chtalyst nitrobenzene compounds are utilized, selective reduction generates arylamine.2015,
Vicente et al. (Chem.Eng.J, 2015,261:53-59.) is supported on the titanium dioxide of Copper-cladding Aluminum Bar using Nano silver grain
Catalyst restores p-nitrophenol；2006, Zhejiang University (CN1321118C [P] .2006-1) was in preparation 5- azepine Yin
During diindyl, precursor is needed through 3- decil alkenyl -4- nitropyridine nitrogen oxides using palladium/carbon as catalyst
Reduction obtains corresponding amine；2013, Suzhou Yong Jian biological medicine Co., Ltd (CN103265457A [P] .2013-08-28)
Have found a kind of using palladium/carbon as catalyst, hydrogen is that reducing agent is catalyzed reduction synthesis (R) -4- aminophenethyl-(2- hydroxyl
Base -2- phenethyl)-t-butyl carbamate synthetic method；2015, He'nan Normal University (CN104892427A [P]
.2015-09-09 the preparation method for) finding a kind of amino phenyl ethylamine, uses p-nitrophenyl ethyl alcohol for raw material, first through catalytic hydrogenation
The contraposition nitro of p-nitrophenyl ethyl alcohol is reduced into amino, is then protected through Boc acid anhydrides to bit amino, hydroxyl again with sulfonating chlorinating
It closes object generation substitution reaction and obtains sulfoacid compound, then by amination, finally slough Boc group and obtain p-aminophenyl ethamine.On
Stating preparation method can effectively prepare aromatic amine, but there is also many problems, include used in catalyst very
Perhaps catalyst preparation is very troublesome also or be that reaction condition is very harsh for valuableness, and needing could be complete under high pressure hydrogen
At.These all limit the popularization and utilization of existing technology of preparing industrially.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of cobalt sulphur codope mesoporous carbon and its system
Preparation Method and application, the cobalt sulphur codope mesoporous carbon manufacturing cost is lower, and is easy preparation, while can be used as and prepare aromatic amine
Catalyst so that aromatic amine can be prepared under normal pressure.
To achieve the above object, the present invention provides the following technical scheme that a kind of cobalt sulphur codope mesoporous carbon, including it is following
Parts by weight substance:
5-10 parts of Citric Acid Mono；
3-7 parts of magnesium nitrate hexahydrate；
1-3 parts of cobalt salt.
As a further improvement of the present invention, the cobalt salt is any one in cobalt sulfate and sulfamic acid cobalt.
As a further improvement of the present invention, a kind of preparation method of cobalt sulphur codope mesoporous carbon, comprising the following steps:
Step 1: required substance is weighed according to formula, Citric Acid Mono and magnesium nitrate hexahydrate are first added to deionized water
In, stirring and dissolving forms solution, then the solution is placed in baking oven and is reacted, and presoma is made；
Step 2: presoma and cobalt salt are stirred, and form mixture；Then under nitrogen protection by mixture, put
Enter in atmosphere furnace and is calcined；It after having calcined, is cooled to room temperature, obtains cobalt sulphur codope mesoporous carbon.
As a further improvement of the present invention, it is placed in oven temperature when reacting in baking oven in the step 1 and is set as 80-
150 DEG C, reaction time 12-36h.
As a further improvement of the present invention, atmosphere furnace temperature setting is 700-900 when being calcined in the step 2
DEG C, calcination time 0.5-3h.
As a further improvement of the present invention, the cobalt sulphur codope mesoporous carbon is as the catalysis for preparing aromatic amine compounds
Agent.
As a further improvement of the present invention, the cobalt sulphur codope mesoporous carbon is as catalyst method particularly includes: by nitre
Base benzene ring type compounds and hydrazine hydrate react 4-24h at 50-70 DEG C, obtained production under the catalysis of cobalt sulphur codope mesoporous carbon
Object is filtered again, extracts, washes, and then dries, and finally obtains aromatic amine compounds.
As a further improvement of the present invention, the nitro benzene ring type compounds are to have a nitro substituent on phenyl ring,
Have R base substituent group at least one position on except the other positions for replacing nitro simultaneously, the R base be H, C1-C6 alkoxy,
Any one in halogen, C1-C6 alkyl, aryl and NR1R2, naphthalene nucleus, wherein R1, R2 H, C1-C6 alkyl, benzyl or aryl
In any one.
As a further improvement of the present invention, nitro benzene ring type compounds and hydrazine hydrate are reacted in a solvent, described
Solvent is any one in toluene, water, ethyl alcohol, acetonitrile, methylene chloride and hexamethylene.
As a further improvement of the present invention, the molar ratio of nitro benzene ring type compounds and hydrazine hydrate dosage is 1:1.5-1:
3；The molar ratio of nitro benzene ring type compounds and cobalt sulphur codope mesoporous carbon dosage is 1:0.05-1:0.2.
Beneficial effects of the present invention: by the way that using Citric Acid Mono, magnesium nitrate hexahydrate and cobalt salt as raw material, preparation method is simple
Single, manufacturing cost is low, easy to spread, can be manufactured on a large scale；The mesoporous carbon product of cobalt sulphur codope prepared simultaneously is steady
Qualitative height, and using it can be used to prepare aromatic amine compounds；When preparing aromatic amine compounds, reaction is easy to grasp
Make, can be carried out sound response at normal pressure, 50-70 DEG C, reaction condition compared to the prior art in generation method more hold
Easily realize；The applicability of the cobalt sulphur codope meso-porous carbon material is wide simultaneously, can all play to a variety of nitro benzene ring type compounds
Good catalytic effect substantially reduces the reaction time, and maximum output can achieve 98%, compared to the prior art in it is general
Preparation method, yield are significantly increased, and economic benefit is higher.
Detailed description of the invention
Fig. 1 is the detection figure of cobalt sulphur codope meso-porous carbon material made from embodiment 1 in the present invention；Wherein 1a is scanning electricity
Mirror figure (SEM)；1b is transmission electron microscope picture (TEM)；1c is high power transmission electron microscope picture (HRTEM)；1d is adsorption desorption curve.
Fig. 2 is the XPS figure of cobalt sulphur codope meso-porous carbon material made from the embodiment of the present invention 1.
Specific embodiment
Embodiment 1: the preparation method of the cobalt sulphur codope mesoporous carbon specifically:
4g Citric Acid Mono and 2.5g magnesium nitrate hexahydrate are added in the deionized water of 10mL, with the speed of 200rad/min
Degree stirring 15min, forms solution, is then put into the solution in 120 DEG C of baking oven, place 24 hours, obtain foam-like
Solid (presoma)；Presoma obtained is mixed with 1g cobalt sulfate with the speed stirring 10min of 300rad/min,
It forms mixture then under nitrogen protection by mixture to be placed in atmosphere furnace and calcine 1 hour under the conditions of 800 DEG C, calcine
After be cooled to 25 DEG C, obtain cobalt sulphur codope mesoporous carbon (SMC-Co).
Embodiment 2: the nitrobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By nitrobenzene (1mmol, 104ul), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol, 146ul) is once
It is added in the reaction tube of 20mL, in 60 DEG C of reaction 6h.Product is extracted with ethyl acetate, then is filtered, extracts, washes, so
After dry, finally obtain the aniline of brown color, yield 98%.1H NMR(500MHz,CDCl3) δ 7.12 (t, J=7.5Hz,
2H), δ 6.73 (t, J=7.5Hz, 1H), δ 6.61 (d, J=7.5Hz, 2H), δ 3.56 (s, 2H)13C NMR(500MHz,
CDCl3)δ146.3,129.1,118.3,114.9。
Embodiment 3: the para-methylnitrobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By para-methylnitrobenzene (1mmol, 0.137mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 6h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain lurid para-totuidine, yield 96%.1H NMR(500MHz,CDCl3)δ6.99
(d, J=8Hz, 2H), δ 6.63 (d, J=8Hz, 2H), δ 3.55 (s, 2H), δ 2.27 (s, 3H)13C NMR(500MHz,CDCl3)
δ143.8,129.7,127.7,115.2,20.38.
Embodiment 4: the ortho-methylnitrobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By ortho-methylnitrobenzene (1mmol, 0.137mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 6h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtained lurid ortho-aminotoluene, yield 96%.1H NMR(500MHz,CDCl3)δ
7.09 (t, J=8Hz, 2H), δ 6.77 (t, J=8Hz, 1H), δ 6.71 (d, J=8Hz, 2H), δ 3.62 (s, 2H), δ 2.21 (s,
3H).13C NMR(500MHz,CDCl3)δ144.5,130.3,126.9,122.2,118.5,114.8,17.2.
Embodiment 5: the meta-methylnitrobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By ortho-methylnitrobenzene (1mmol, 0.137mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 6h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain the meta-aminotoluene of colorless oil, yield 93%.1H NMR(500MHz,CDCl3)δ
7.09 (t, J=7.5Hz, 1H), δ 6.62 (d, J=7.5Hz, 1H), δ 6.54-6.52 (m, 2H), δ 3.61 (s, 2H), δ 2.30
(s,3H).13C NMR(500MHz,CDCl3)δ146.3,139.0,129.1,119.4,115.9,112.2,21.34.
Embodiment 6: the p-Nitrobromobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
Will be to bromo nitrobenzene (1mmol, 0.202mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 8h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain the para-bromoaniline of grey, yield 92%.1H NMR(500MHz,CDCl3)δ7.20
(d, J=8.5Hz, 2H), δ 6.52 (d, J=8.5Hz, 2H), 3.63 (s, 2H)13C NMR(500MHz,CDCl3)δ147.7,
130.5,122.9,121.2,117.7,113.6.
Embodiment 7: the o-bromonitrobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By o-bromonitrobenzene (1mmol, 0.202mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 8h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, the o-bromoaniline of finally obtained white, yield 93%.1HNMR(500MHz,CDCl3)δ7.42
(d, J=8Hz, 1H), δ 7.12 (t, J=8Hz, 1H), δ 6.77 (d, J=8Hz, 1H), δ 6.64 (t, J=8Hz, 1H), 4.10
(s,2H).13C NMR(500MHz,CDCl3)δ144.0,132.5,128.3,119.3,115.7,109.2.
Embodiment 8: the m-bromonitrobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By m-bromonitrobenzene (1mmol, 0.202mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 8h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain lurid m-bromoaniline, yield 93%.1H NMR(500MHz,CDCl3)δ7.09
(t, J=7.5Hz, 1H), δ 6.62 (d, J=7.5Hz, 1H), δ 6.54-6.52 (m, 2H), δ 3.61 (s, 2H), δ 2.30 (s,
3H).13C NMR(500MHz,CDCl3)δ146.3,139.0,129.1,119.4,115.9,112.2,21.34.
Embodiment 9: the p-fluoronitrobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By p-fluoronitrobenzene (1mmol, 0.141mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 8h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain lurid para-fluoroaniline, yield 92%.1H NMR(500MHz,CDCl3)δ
6.87 (t, J=9Hz, 2H), δ 6.62-6.59 (m, 2H), δ 3.50 (s, 2H)13C NMR(500MHz,CDCl3)δ157.2,
155.3,142.4,116,115.9,115.5,115.4.
Embodiment 10: the parachloronitrobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By parachloronitrobenzene (1mmol, 0.158mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 6h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain lurid parachloroanilinum, yield 98%.1H NMR(500MHz,CDCl3)δ7.10
(d, J=8.5Hz, 2H), δ 6.60 (d, J=8.5Hz, 2H), 3.66 (s, 2H)13C NMR(500MHz,CDCl3)δ144.9,
129.0,123.0,116.2.
Embodiment 11: cobalt sulphur codope mesoporous carbon catalysis to iodonitrobenzene reduction reaction
Will be to iodonitrobenzene (1mmol, 0.249mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, for 24 hours in 70 DEG C of reactions.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain the paraiodoaniline of white, yield 96%.1H NMR(500MHz,CDCl3)δ7.36
(d, J=8.5Hz, 2H), δ 6.41 (d, J=8.5Hz, 2H), 3.63 (s, 2H)13C NMR(500MHz,CDCl3)δ146.0,
137.7,117.1,79.1.
Embodiment 12: cobalt sulphur codope mesoporous carbon catalysis to methoxy nitrobenzene reduction reaction
Will be to methoxy nitrobenzene (1mmol, 0.153mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 8h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain lurid P-nethoxyaniline, yield 87%.1H NMR(500MHz,CDCl3)δ
6.76 (d, J=9Hz, 2H), δ 6.64 (d, J=9Hz, 2H), δ 3.75 (s, 3H), δ 3.44 (s, 2H)13C NMR(500MHz,
CDCl3)δ152.6,139.9,116.3,114.7,55.6.
Embodiment 13: the 1,3- dimethyl -2- nitrobenzene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By 1,3- dimethyl -2- nitrobenzene (1mmol, 0.151mg), SMC-Co (20mg), water (2mL), hydrazine hydrate
(2.4mmol, 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 8h.Product is extracted with ethyl acetate, then into
Row filtering, extraction, washing, then dry, finally obtain lurid 1,3- dimethyl -2- aniline, yield 94%.1H NMR
(500MHz,CDCl3) δ 7.03 (d, J=7.5Hz, 2H), δ 6.74 (d, J=7.5Hz, 1H), δ 3.56 (s, 2H), δ 2.26 (s,
6H).13CNMR(500MHz,CDCl3)δ142.6,128.1,121.6,117.9,17.5.
Embodiment 14: the 3- nitropyridine reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By 3- nitropyridine (1mmol, 0.124mg), SMC-Co (20mg), toluene (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 4h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain lurid 3- aminopyridine, yield 82%.1H NMR(500MHz,DMSO)δ
7.95 (d, J=3.5Hz, 1H), δ 7.73 (d, J=3.5Hz, 1H), δ 7.03 (dd, J1=3.5Hz, J2=8.5Hz, 1H), δ
6.93 (d, J=8.5Hz, 1H), δ 5.28 (s, 2H)13C NMR(500MHz,DMSO)δ145.0,136.9,136.2,123.8,
120.1.
Embodiment 15: the 1- nitronaphthalene reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By 1- nitronaphthalene (1mmol, 0.173mg), SMC-Co (30mg), water (2mL), hydrazine hydrate (2.4mmol, 146ul)
It is once added in the reaction tube of 20mL, in 60 DEG C of reaction 20h.Product is extracted with ethyl acetate, then is filtered, extracts, water
It washes, then dries, finally obtain the 1- amino naphthalenes of white, yield 90%.1H NMR (500MHz, DMSO) δ 8.14 (d, J=
8Hz, 1H), δ 7.75 (d, J=8Hz, 1H), δ 7.43-7.37 (m, 2H), δ 7.25 (t, J=8Hz, 1H), δ 7.12 (d, J=
8Hz, 1H), δ 6.77 (d, J=8Hz, 1H), δ 5.76 (s, 2H)13C NMR(125MHz,DMSO)δ144.7,134.3,127.9,
126.8,125.5,123.7,122.9,122.4,115.6,107.7.
Embodiment 16: the p-nitrophenyl formamide reduction reaction of cobalt sulphur codope mesoporous carbon catalysis
By p-nitrophenyl formamide (1mmol, 0.166mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,
It 146ul) is once added in the reaction tube of 20mL, in 60 DEG C of reaction 8h.Product is extracted with ethyl acetate, then is filtered, extracts
It takes, wash, then dry, finally obtain the Para Amino Benzamide of white, yield 97%.1H NMR(500MHz,DMSO)δ
7.63 (d, J=6Hz, 3H), δ 6.96 (s, 1H), δ 6.55 (d, J=6Hz, 2H), δ 5.63 (s, 2H)13C NMR(500MHz,
DMSO)δ167.5,153.2,131.3,117.0,112.6.
It extracts in the present invention and product is extracted using ethyl acetate as extract liquor.
The molecular structural formula of the nitro benzene ring type compounds isThe R base is H, C1-C6 alkoxy, halogen
Any one in element, C1-C6 alkyl, aryl and NR1R2, naphthalene nucleus, wherein R1, R2 H, C1-C6 alkyl, in benzyl or aryl
Any one.
Sample made from implementing one is detected with scanning electron microscope, transmission electron microscope and high magnification transmission electron microscope respectively, is obtained
To Fig. 1 a, Fig. 1 b and Fig. 1 c；From Fig. 1 a, 1b, 1c simultaneously combine 1d it is found that sample made from the present embodiment 1 is multilayer chip structure.
Sample made from embodiment 1 is detected with x-ray photoelectron spectroscopy, obtains Fig. 2；As shown in Figure 2, implement
It is 9.30% that sulfur content in sample, which is made, in example 1, cobalt content 12.00%, carbon content 28.59%.
A kind of cobalt sulphur codope mesoporous carbon of the invention and its preparation method and application is preparing cobalt sulphur codope mesoporous carbon
When, using Citric Acid Mono, magnesium nitrate hexahydrate and cobalt salt as raw material, since element sulphur can be doped into, so cobalt salt selects
Cobalt sulfate and sulfamic acid cobalt；Using deionized water as solvent, first Citric Acid Mono and magnesium nitrate hexahydrate are stirred,
It is placed in after mixing in the baking oven that temperature is 80-150 DEG C, reacts 12-36h, presoma can be obtained after reaction, it is a kind of
Foaming solid；Then the cobalt salt of presoma obtained and sulfur-bearing is stirred, then enters 700- in the protection down of nitrogen
0.5-3h is calcined in 900 DEG C of atmosphere furnace, calcining purpose is to form mesoporous carbon, improves catalytic effect of the invention；Calcining terminates
Afterwards, it is cooled to room temperature, so that it may obtain cobalt sulphur codope mesoporous carbon.The preparation method is simple, and cost of material is low, easy to spread,
It is suitble to extensive manufacture.
The cobalt sulphur codope mesoporous carbon may be used as preparing the catalyst of aromatic amine compounds；Preparing aromatic amine
When closing object, operation is simple, and operation is simple；In normal pressure, temperature is that can be carried out sound response at 50-70 DEG C, instead
Answer condition compared to the prior art in generation method be easier realize；Its reaction formula isR can be all kinds of substituent groups in 2-, 3- or the 4- of phenyl ring.R can
To be H, C1-C6 alkoxy, halogen (fluorine, chlorine, bromine), C1-C6 alkyl, aryl, NR1R2 (R1, R2 H, C1-C6 alkyl, benzyl
Or aryl etc.).R also represents the aromatic ring of benzo, such as naphthalene nucleus.The aryl is recommended as phenyl, and (substituent group is C1- to substituted-phenyl
C6 alkyl, C1-C6 alkoxy), naphthalene etc..It, can to illustrate the applied widely of the cobalt sulphur codope meso-porous carbon material
Good catalytic effect is all played to a variety of nitro benzene ring type compounds, substantially reduces the reaction time, maximum output can reach
To 98%, compared to the prior art in general preparation method, yield is significantly increased, and economic benefit is higher.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of cobalt sulphur codope mesoporous carbon, it is characterised in that: including following parts by weight substance:
5-10 parts of Citric Acid Mono；
3-7 parts of magnesium nitrate hexahydrate；
1-3 parts of cobalt salt.
2. a kind of cobalt sulphur codope mesoporous carbon according to claim 1, it is characterised in that: the cobalt salt is cobalt sulfate
With any one in sulfamic acid cobalt.
3. a kind of preparation method of cobalt sulphur codope mesoporous carbon according to claim 1 or 2, it is characterised in that: including with
Lower step:
Step 1: required substance is weighed according to formula, first Citric Acid Mono and magnesium nitrate hexahydrate are add to deionized water, stirred
Dissolution is mixed, solution is formed, then the solution is placed in baking oven and is reacted, presoma is made；
Step 2: presoma and cobalt salt are stirred, and form mixture；Then under nitrogen protection by mixture, it is put into gas
It is calcined in atmosphere furnace；It after having calcined, is cooled to room temperature, obtains cobalt sulphur codope mesoporous carbon.
4. a kind of preparation method of cobalt sulphur codope mesoporous carbon according to claim 3, it is characterised in that: the step 1
In be placed in baking oven react when oven temperature be set as 80-150 DEG C, reaction time 12-36h.
5. a kind of preparation method of cobalt sulphur codope mesoporous carbon according to claim 3, it is characterised in that: the step 2
In when being calcined atmosphere furnace temperature setting be 700-900 DEG C, calcination time 0.5-3h.
6. according to claim 1 to a kind of purposes of cobalt sulphur codope mesoporous carbon described in 5 any one, it is characterised in that: should
Cobalt sulphur codope mesoporous carbon is as the catalyst for preparing aromatic amine compounds.
7. a kind of purposes of cobalt sulphur codope mesoporous carbon according to claim 6, it is characterised in that: the cobalt sulphur codope is situated between
Hole carbon is as catalyst method particularly includes: is catalyzed nitro benzene ring type compounds and hydrazine hydrate in cobalt sulphur codope mesoporous carbon
Under, 4-24h is reacted at 50-70 DEG C, obtained product is filtered again, extracts, washes, and then dries, and finally obtains fragrance
Aminated compounds.
8. a kind of purposes of cobalt sulphur codope mesoporous carbon according to claim 7, it is characterised in that: the nitro phenyl ring class
Compound is to have a nitro substituent on phenyl ring, while having R at least one position on except the other positions for replacing nitro
Base substituent group, the R base are H, C1-C6 alkoxy, halogen, C1-C6 alkyl, any one in aryl and NR1R2, naphthalene nucleus,
Wherein R1, R2 H, C1-C6 alkyl, any one in benzyl or aryl.
9. a kind of purposes of cobalt sulphur codope mesoporous carbon according to claim 8, it is characterised in that: nitro phenyl ring class chemical combination
Object and hydrazine hydrate are reacted in a solvent, and the solvent is appointing in toluene, water, ethyl alcohol, acetonitrile, methylene chloride and hexamethylene
It anticipates one kind.
10. a kind of purposes of cobalt sulphur codope mesoporous carbon according to claim 9, it is characterised in that: nitro phenyl ring class
The molar ratio for closing object and hydrazine hydrate dosage is 1:1.5-1:3；Nitro benzene ring type compounds and cobalt sulphur codope mesoporous carbon dosage
Molar ratio is 1:0.05-1:0.2.
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| CN113471455A (en) * | 2021-07-01 | 2021-10-01 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
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