CN107376970A - Monatomic porous C catalyst of iron nitrating and preparation method and application - Google Patents
Monatomic porous C catalyst of iron nitrating and preparation method and application Download PDFInfo
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- CN107376970A CN107376970A CN201710610206.XA CN201710610206A CN107376970A CN 107376970 A CN107376970 A CN 107376970A CN 201710610206 A CN201710610206 A CN 201710610206A CN 107376970 A CN107376970 A CN 107376970A
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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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/18—Halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
Abstract
The invention provides a kind of monatomic porous C catalyst of iron nitrating and preparation method and application, the catalyst is using monatomic iron as active component, using nitrating porous carbon materials as carrier, and iron is scattered in nitrating porous carbon materials carrier surface and inside with monatomic form, wherein, counted using the gross weight of the monatomic porous C catalyst of iron nitrating as 100%, it contains 1.0 3.0wt% iron and 4.0 9.0wt% nitrogen.Present invention also offers the method using the monatomic iron nitrating porous carbon catalyst nitrogen-containing heterocycle compound dehydrogenation oxidation reaction, and application of the monatomic porous C catalyst of iron nitrating in catalysis nitrogen-containing heterocycle compound dehydrogenation oxidation reaction.There is the catalyst excellent catalytic effect, catalytic reaction product is analyzed using GC MS after terminating, and analysis result shows that no coupling product produces, and the catalyst recycle 5 times after activity reduced without obvious.
Description
Technical field
The present invention relates to a kind of monatomic porous C catalyst of iron nitrating and preparation method and application, belong to monatomic and urge
Agent technical field.
Background technology
Nitrogen-containing heterocycle compound has extensive bioactivity, and it also has less toxic, efficient, environment-friendly, structure in addition
The features such as various；And the dehydrogenation oxidation of nitrogen-containing heterocycle compound organic synthesis field be basic and important reaction type it
One, the reaction can synthesize a variety of high added value compounds；Quinoline is as the typical generation in nitrogen-containing heterocycle compound this quasi-molecule
Table, it is the synthesis presoma of many biologies and drug molecule；And the derivative of quinoline serves many purposes, as 8-hydroxyquinoline can
For use as a luminescent material, 6- chloroquinolines can be used as pesticide synthesis intermediate etc..
At present, this area by dehydrogenation oxidation reaction with suitable raw material largely on preparing corresponding quinoline and quinoline
The report of quinoline derivant, such as：
Document 1 (Yamaguchi, R.；Ikeda,C.；Takahashi,Y.；Fujita,K.Journal of the
American Chemical Society 2009,131 (24), 8410.) homogeneous catalysis using metal iridium as activated centre is used
2- methyl tetrahydroquinolines are converted to 2- methylquinolines by agent, are flowed back 20 hours under an argon atmosphere, and the yield of products therefrom is
100%, TON value are 37；
Document 2 (Tseng, K.N.T.；Rizzi,A.M.；Szymczak,N.K.Journal of the American
Chemical Society 2013,135 (44), 16352-5.) to use using metal Ru be the homogeneous catalyst in activated centre by Yin
Diindyl quinoline is converted to indoles, and reaction temperature is 110 DEG C, and the time is 24 hours, and the yield of products therefrom is that 81%, TON values are 81；
Document 3 (Chakraborty, S.；Brennessel,W.W.；Jones,W.D.Journal of the
American Chemical Society 2014,136 (24), 8564-8567.) use using metallic iron as the equal of activated centre
Tetrahydroquinoline is converted to quinoline by phase catalyst, and reaction temperature is 140 DEG C, and the time is 30 hours, and the yield of products therefrom is
69%, TON value are 23；
Document 4 (Jawale, D.V.；Gravel,E.；Shah,N.；Dauvois,V.；Li,H.；Namboothiri,
I.N.N.；Doris, E.Chemistry-A European Journal 2015,21 (19), 7039-7042.) use with metal
Rhodium is activated centre, and tetrahydroquinoline is converted to quinoline by carbon pipe for the heterogeneous catalysis (RhCNT) of carrier, and reaction temperature is room
Temperature, time are 10 hours, and under the collaboration of 10mol% co-catalysts, the yield of products therefrom is 95%, TON values 95；
Document 5 (Sun, X.-T.；Zhu,J.；Xia,Y.-T.；Wu,L.ChemCatChem 2017,9(13),2463–
2466.) use the heterogeneous catalysis (Pd NPs) using Metal Palladium particle as activated centre that tetrahydroquinoline is converted into quinoline, instead
It is room temperature to answer temperature, and the time is 18 hours, and in the presence of 8 times are measured oxidant tert-Butanol peroxide, the yield of products therefrom is
91%, TON value are 22；
Document 6 (Iosub, A.V.；Stahl, S.S.Organic Letters 2015,17 (18), 4404-4407.) adopt
Tetrahydroquinoline is converted into quinoline for the heterogeneous catalysis in activated centre to cobaltosic oxide, reaction temperature is 60 DEG C, when
Between be 6 hours, under oxygen atmosphere and the synergy of potassium carbonate, the yield of products therefrom is that 85%, TON values are 47；
Document 7 (Cui, X.；Li,Y.；Bachmann,S.；Scalone,M.；Surkus,A.-E.；Junge,K.；Topf,
C.；Beller,M.Journal of the American Chemical Society 2015,137(33),10652-
10658.) use using metal iron oxide particle as activated centre, porous carbon is heterogeneous catalysis (the FeOx NGr- of carrier
C tetrahydroquinoline) is converted into quinoline, reaction temperature is 100 DEG C, and the time is 12 hours, under 1MPa air effects, products therefrom
Yield be that 90%, TON values are 36；
Document 8 (Damodara, D.；Arundhathi,R.；Likhar,P.R.Advanced Synthesis&
Catalysis2014,356 (1), 189-198.) use heterogeneous catalysis (Cu/ using metallic copper particle as activated centre
Al2O3) tetrahydroquinoline is converted into quinoline, reaction temperature is 120 DEG C, and the time is 8 hours, and the yield of products therefrom is 94%,
TON values are 30；
As can be seen here, homogeneous noble metal is confined to the used catalyst of nitrogen-containing heterocycle compound dehydrogenation oxidation reaction at present to urge more
Agent such as iridium, palladium etc., such catalyst cost is high and is unfavorable for catalyst recovery；And non-precious metal catalyst dosage is big, temperature
It is high and less efficient, oxidant such as hydrogen peroxide or tert-Butanol peroxide are often also relied on, the expansion performance to derivative is paid no attention to
Think.
For the metallic catalyst of high capacity amount, only have only a few metal active constituent to play catalysis in catalytic reaction process
Effect, comparatively speaking, each metallic atom " is pitted one against tenEvery man is worth ten " as the monatomic catalysis of active sites in efficiency, and traditional
The metal utilization ratio of load type metal catalyst is well below desirable level.For noble metal, heavy dose makes
With catalyst cost is undoubtedly added, it is unfavorable for carrying out scale application in the industrial production.Therefore, in order to send out to greatest extent
The catalytic efficiency of metal is waved, reduces manufacturing cost, preparing monoatomic metal catalyst turns into the primary selection of researcher.
In summary, there is provided more excellent porous C catalyst of monoatomic metal nitrating of a kind of performance and preparation method thereof
And use it for being catalyzed the reaction of nitrogen-containing heterocycle compound dehydrogenation oxidation as the technical problem of this area urgent need to resolve.
The content of the invention
In order to solve the shortcomings that above-mentioned and deficiency, it is an object of the invention to provide a kind of monatomic iron nitrating porous carbon to urge
Agent.
The present invention also aims to provide the preparation method of the above-mentioned monatomic porous C catalyst of iron nitrating.
The present invention also aims to provide using above-mentioned monatomic iron nitrating porous carbon catalyst nitrogen-containing hetero cyclisation
The method of compound dehydrogenation oxidation reaction.
The present invention also aims to provide the above-mentioned monatomic porous C catalyst of iron nitrating in catalysis nitrogen heterocyclic ring chemical combination
Application in the reaction of thing dehydrogenation oxidation.
To reach above-mentioned purpose, the present invention provides a kind of monatomic porous C catalyst of iron nitrating, and the catalyst is with single original
Sub- iron is active component, and using nitrating porous carbon materials as carrier, and iron is scattered in nitrating porous carbon materials with monatomic form and carried
Body surface face and inside, wherein, counted using the gross weight of the monatomic porous C catalyst of iron nitrating as 100%, it contains 1.0-
3.0wt% iron and 4.0-9.0wt% nitrogen.
In the described monatomic porous C catalyst of iron nitrating, active component iron is scattered in monatomic form (Fe-N)
Nitrating porous carbon materials carrier surface and inside and iron-free particle aggregation.
According to specific embodiments of the present invention, the specific surface area of the monatomic porous C catalyst of iron nitrating is 800-
1000m2/ g, aperture 10-14nm, pore volume 2-4cm3/g。
Present invention also offers the preparation method of the monatomic porous C catalyst of iron nitrating, it comprises the following steps：
(1) molysite, nitrogenous organic ligand and template are well mixed in a solvent, then remove solvent, dry
To a solid mixture；
(2) solid mixture is calcined 0.5-4 hours at 600-1000 DEG C, obtain composite；
(3) acid treatment is carried out to the composite, obtains the monatomic porous C catalyst of iron nitrating.
According to specific embodiments of the present invention, in the preparation method of the described monatomic porous C catalyst of iron nitrating,
Preferably, the template includes porous flake hexagon magnesia；
It is highly preferred that the specific surface area of the porous flake hexagon magnesia is 100-300m2/ g, two-dimensional slice footpath size
For 200-400nm；
It is further preferred that the porous flake hexagon magnesia is through the following steps that be prepared：Will oxidation
Magnesium dust boils in water and kept for 12-72 hours, by obtained solid after drying, then it is small in 400-800 DEG C of calcining 1-4
When, obtain described porous flake hexagon magnesia；
Most preferably, temperature after drying, 400- is risen to 5-25 DEG C/min heating rate by the solid from room temperature
800℃.Wherein, product can be cooled to room temperature after drying, then again with 5-25 DEG C/min heating rate by product temperatur
Calcined after rising to 400-800 DEG C from room temperature.
According to specific embodiments of the present invention, in the preparation method of the described monatomic porous C catalyst of iron nitrating,
Preferably, the molysite includes one or more of combinations in ferric sulfate, ferric nitrate, iron chloride and ferrous acetate.
According to specific embodiments of the present invention, in the preparation method of the described monatomic porous C catalyst of iron nitrating,
Preferably, the nitrogenous organic ligand includes 2,2'- bipyridyls, pyridine, phenanthrolene, 2,2':6', 2 "-ter cycloheptapyridine, 2,
One or more of combinations in (2- benzimidazolyls) pyridines of 6- bis- and pyrroles.
According to specific embodiments of the present invention, in the preparation method of the described monatomic porous C catalyst of iron nitrating,
Preferably, the mass ratio of the molysite employed in step (1), nitrogenous organic ligand and template is 1:0.5-4:1.5-6.
According to specific embodiments of the present invention, in the preparation method of the described monatomic porous C catalyst of iron nitrating,
Preferably, the solvent in step (1) includes one or more of combinations in ethanol, water, acetone and ethyl acetate.
According to specific embodiments of the present invention, in the preparation method of the described monatomic porous C catalyst of iron nitrating,
Preferably, calcining is carried out under inert gas shielding described in step (2), and the inert gas includes argon gas and/or nitrogen
Gas.
According to specific embodiments of the present invention, in the preparation method of the described monatomic porous C catalyst of iron nitrating,
Preferably, solid mixture temperature is risen to 600-1000 DEG C from room temperature with 5-25 DEG C/min heating rate in step (2).This
Invention porous flake hexagon magnesium oxide template agent used has the function that pore-creating, therefore different calcining heats at high temperature
The structure of preparation-obtained catalyst can be caused different, and then make it that the activity of the catalyst is different.
According to specific embodiments of the present invention, in the preparation method of the described monatomic porous C catalyst of iron nitrating,
To remove template, its another object removes to be generated the first purpose of acid treatment described in step (3) in cracking process
Fe3C particles；Wherein, removing the acid used in template process includes the not acid with template generation sulfuric acid magnesium precipitate, removes impurity
Acid used in particle includes not volatile acid；Preferably, the acid treatment specifically includes following steps：Watery hydrochloric acid is used first
The composite is handled to remove template, then using dilute sulfuric acid in a heated condition to gained after watery hydrochloric acid processing
Product is handled to remove impurity particle.
In addition, the application does not make specifically to specific concentration, processing time and the heating-up temperature of watery hydrochloric acid and dilute sulfuric acid
Ask, those skilled in the art can need Reasonable adjustment above-mentioned parameter according to operation, as long as ensureing that the mesh of the present invention can be realized
；In the specific embodiment of the invention, the acid treatment specifically includes following steps：Concentration is used first as 0.1M's
Watery hydrochloric acid to the composite handle 30min to remove template, then it is 1M dilute sulfuric acid at 80 DEG C to use concentration
Products therefrom after watery hydrochloric acid processing is carried out handling 3h to remove impurity particle.
Present invention also offers one kind to use the monatomic iron nitrating porous carbon catalyst nitrogen-containing heterocycle compound
The method of dehydrogenation oxidation reaction, this method comprise the following steps：
The catalyst is well mixed in a solvent with nitrogen-containing heterocycle compound, and stirred under oxygen or air atmosphere
Dehydrogenation oxidation reaction is carried out under the conditions of mixing；
Wherein it is preferred to the mass ratio of the catalyst and nitrogen-containing heterocycle compound is 1:1.5-4.0, catalyst with it is molten
The mass ratio of agent is 0.01-0.03:1；
It is further preferred that the solvent is included in acetonitrile, ethanol, ethyl acetate, toluene, acetone, hexamethylene and normal heptane
A kind of combination that can be several；
It is further preferred that reaction temperature is 40-80 DEG C, the reaction time is 5-18 hours.
According to specific embodiments of the present invention, in the described method, the application does not want to the specific rotating speed of stirring
Asking, those skilled in the art can need the rotating speed that Reasonable adjustment stirs according to operation, as long as ensureing that raw material is well mixed,
In specific implementation process of the present invention, speed of agitator can be 120-300rpm.
According to specific embodiments of the present invention, in the described method, it is preferable that the nitrogen-containing heterocycle compound includes
1,2,3,4- tetrahydroquinolines and its derivative, 1,2,3,4- tetrahydroisoquinolines and its derivative or 1,2,3,4- tetrahydroquinoxalines and
Any of its derivative；
It is highly preferred that described 1, the derivatives of 2,3,4- tetrahydroquinolines include methyl, hydroxyl, methoxyl group, halogen, nitro and
Carboxyl is respectively in the 1,2,3,4- tetrahydroquinolines of 5,6,7, No. 8 position substitutions；
It is more preferred still that described 1, the derivative of 2,3,4- tetrahydroisoquinolines includes methyl, hydroxyl, methoxyl group, halogen, nitre
Base and carboxyl are respectively in the 1,2,3,4- tetrahydroisoquinolines of 5,6,7, No. 8 position substitutions；
It is more preferred still that described 1, the derivative of 2,3,4- tetrahydroquinoxalines includes methyl, hydroxyl, methoxyl group, halogen, nitre
Base and carboxyl are respectively in the 1,2,3,4- tetrahydroquinoxalines of 5,6,7, No. 8 position substitutions.
In the specific embodiment of the invention, described 1, the derivatives of 2,3,4- tetrahydroquinolines includes 6- methyl isophthalic acids, and 2,3,
4- tetrahydroquinolines, 2- methyl isophthalic acids, 2,3,4- tetrahydroquinolines, 8- hydroxyl -1,2,3,4- tetrahydroquinolines, 6- hydroxyls -1,2,3,4- four
Hydrogen quinoline, 7- hydroxyl -1,2,3,4- tetrahydroquinolines, 6- methoxyl group -1,2,3,4- tetrahydroquinolines, the fluoro- 1,2,3,4- tetrahydrochysenes quinolines of 6-
The chloro- 1,2,3,4- tetrahydroquinolines of quinoline, 6-, the bromo- 1,2,3,4- tetrahydroquinolines of 6-, 6- nitro -1,2,3,4- tetrahydroquinolines or 6- carboxylics
Any of base -1,2,3,4- tetrahydroquinolines.
Present invention also offers the monatomic porous C catalyst of iron nitrating in catalysis nitrogen-containing heterocycle compound dehydrogenation oxygen
Change the application in reaction.
At present, in the existing method for preparing monatomic catalyst, prepared by material is limited by yield and load capacity more.
The application is raw material using the inorganic salts and itrogenous organic substance of iron, prepares organometallic complex presoma, and utilize porous MgO
For template, prevent metallic atom to reunite, then the monatomic catalyst of transition metal is prepared by high-temperature heat treatment.It is monatomic to urge
Agent has single scattered active sites, avoids the generation of side reaction and the follow-up place such as purification purifying that accessory substance may be brought
Reason process and potential environmental problem, so as to save post-processing expense, make production process more economically environmentally friendly, reach " green
The purpose of catalysis ".In addition, the monatomic iron nitrating porous carbon catalyst nitrogen heterocyclic ring chemical combination being prepared using the application
Thing dehydrogenation oxidation reacts, and the catalyst has excellent catalytic effect, and catalytic reaction terminates to divide product using GC-MS
Analysis, analysis result show that no coupling product produces, and the catalyst recycle 5 times after activity reduced without obvious.
Brief description of the drawings
The TEM figures for the monatomic porous C catalyst of iron nitrating that Fig. 1 is provided by the embodiment of the present invention 2；
Fig. 2 is the HAADF-STEM figures for the monatomic porous C catalyst of iron nitrating that the embodiment of the present invention 2 provides；
Fig. 3 is the XRD for the monatomic porous C catalyst of iron nitrating that the present invention is obtained using different acid treatment processes；
The isothermal adsorption line chart for the monatomic porous C catalyst of iron nitrating that Fig. 4 is provided by the embodiment of the present invention 2；
The graph of pore diameter distribution for the monatomic porous C catalyst of iron nitrating that Fig. 5 is provided by the embodiment of the present invention 2；
The XPS phenograms for the monatomic porous C catalyst of iron nitrating that Fig. 6 is provided by the embodiment of the present invention 2；
Fig. 7 is the recycling performance curve map of catalyst B in application examples 2 of the present invention；
Fig. 8 is the GC spectrograms of product in application examples 2 of the present invention；
Fig. 9-10 is the test mass spectrogram for internal standard-dodecane that retention time is 4.223 and spectrum storehouse mass spectrogram in Fig. 8；
Figure 11-12 is the test mass spectrogram for product-quinoline that retention time is 4.463 and spectrum storehouse mass spectrogram in Fig. 8；
Figure 13-14 is the test mass spectrogram for the raw material-1,2,3,4- tetrahydroquinolines that retention time is 4.803 and spectrum in Fig. 8
Storehouse mass spectrogram.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, in conjunction with detail below
Embodiment to technical scheme carry out it is described further below, but it is not intended that to the present invention can practical range limit
It is fixed.
Embodiment 1
A kind of preparation method of the monatomic porous C catalyst of iron nitrating is present embodiments provided, it comprises the following steps：
The preparation of porous flake hexagon magnesium oxide template agent：
Magnesium oxide powder is scattered in deionized water, and 24h is boiled in backflow, and 80 DEG C are dried overnight, by dried product
Room temperature is cooled to, then is warming up to 450 DEG C with 10 DEG C of heating rates per minute and is calcined 60 minutes, obtains the oxidation of porous flake hexagon
Magnesium template, its specific surface area are 200m2/ g, two-dimensional slice footpath size is about 300nm；
The preparation of the monatomic porous C catalyst of iron nitrating：
300mg iron chloride and 500mg 2, the stirring of 2 '-bipyridyl are dissolved in ethanol at room temperature, it is above-mentioned then to add 1g
The magnesium oxide template agent being prepared, 12h is stirred, remove solvent, be dried to obtain precursor mixture (solid mixture)；
Precursor mixture is placed in tube furnace and under argon gas protection with 10 DEG C/min heating rates to 600 DEG C of calcinings
60 minutes, obtain the composite of template, cementite, iron oxide and the monatomic catalyst of iron；
The template of above-mentioned preparation, cementite, iron oxide and the monatomic catalyst composite of iron are placed in watery hydrochloric acid
Stirring 30min in (0.1mol/L), gained solid with dilute sulfuric acid (1mol/L) heating boiling reflux 2h, are consolidated after filtering again
Body, re-dry 12h, the monatomic porous C catalyst of iron nitrating is obtained, is designated as catalyst A；Wherein, catalyst A iron content is
2.19wt%, nitrogen content 8.9wt%, specific surface area 857m2/ g, aperture 10.4nm, pore volume 2.25cm3/g。
Embodiment 2
A kind of preparation method of the monatomic porous C catalyst of iron nitrating is present embodiments provided, it comprises the following steps：
The preparation of porous flake hexagon magnesium oxide template agent：
Magnesium oxide powder is scattered in deionized water, and 24h is boiled in backflow, and 80 DEG C are dried overnight, then per minute with 10 DEG C
Heating rate is warming up to 450 DEG C and is calcined 60 minutes, obtains porous flake hexagon magnesium oxide template agent, its specific surface area is
200m2/ g, two-dimensional slice footpath size is about 300nm；
The preparation of the monatomic porous C catalyst of iron nitrating：
300mg iron chloride and 500mg 2, the stirring of 2 '-bipyridyl are dissolved in ethanol at room temperature, it is above-mentioned then to add 1g
The magnesium oxide template agent being prepared, 12h is stirred, remove solvent, be dried to obtain precursor mixture；
Precursor mixture is placed in tube furnace and under argon gas protection with 10 DEG C/min heating rates to 700 DEG C of calcinings
60 minutes, obtain the composite of template, cementite, iron oxide and the monatomic catalyst of iron；
The template of above-mentioned preparation, cementite, iron oxide and the monatomic catalyst composite of iron are placed in watery hydrochloric acid
Stirring 30min in (0.1mol/L), resulting solid with dilute sulfuric acid (1mol/L) heating boiling reflux 2h, obtain after filtering again
Solid, 12h is dried, the monatomic porous C catalyst of iron nitrating is obtained, is designated as catalyst B, wherein, catalyst B iron content is
1.75wt%, nitrogen content 7.2wt%, specific surface area 910m2/ g, aperture 11.0nm, pore volume 2.49cm3/g；
TEM, HAADF-STEM, XRD, isothermal adsorption and XPS is carried out to catalyst B respectively to test, while in order to investigate
Influence of the different acid treatment processes to gained catalyst performance, to the application composite, gained is solid only after HCl treatment herein
Body has also carried out XRD signs；
Wherein, catalyst B TEM schemes as shown in Figure 1, HAADF-STEM and schemes as shown in Figure 2, different acid treatment process institutes
The obtained porous C catalyst XRD of monatomic iron nitrating as shown in Figure 3, catalyst A isothermal adsorption line chart such as Fig. 4 institutes
Show, graph of pore diameter distribution is as shown in figure 5, XPS spectrum figure is as shown in Figure 6；
From figure 1 it appears that catalyst B is very thin sheet porous material, its surface remains without metallic particles；
From figure 2 it can be seen that under HAADF-STEM patterns, active component iron in catalyst can be clearly observed
It is to exist with monatomic form, the picture that white point is Fe atoms is highlighted in Fig. 2；
From figure 3, it can be seen that there is Fe in cracking process3C particles generations, the process of template agent removing is gone using watery hydrochloric acid
In, the Fe3C particles not disappear, then to remove template after products therefrom using dilute sulfuric acid heat after, this is unstable
Metal carbide particles (Fe3C particles) it is removed, and then obtained the homogeneous porous C catalyst of monatomic Fe2O3 doping；
Figure 4, it is seen that catalyst B adsorption isotherm is IV type curves, it is mesoporous material to show it, further according to
BET methods, the specific surface area that catalyst B can be calculated are 910m2/g；
, can be with further according to BJH methods from figure 5 it can be seen that catalyst B pore-size distributions is unimodal, aperture structure is homogeneous
The aperture that catalyst B is calculated is 11.0nm；
From fig. 6 it can be seen that successfully it is mixed with ferro element and nitrogen in catalyst B.
Embodiment 3
A kind of preparation method of the monatomic porous C catalyst of iron nitrating is present embodiments provided, it comprises the following steps：
The preparation of porous flake hexagon magnesium oxide template agent：
Magnesium oxide powder is scattered in deionized water, and 24h is boiled in backflow, and 80 DEG C are dried overnight, then per minute with 10 DEG C
Heating rate is warming up to 450 DEG C and is calcined 60 minutes, obtains porous flake hexagon magnesium oxide template agent, its specific surface area is
200m2/ g, two-dimensional slice footpath size is about 300nm；
The preparation of the monatomic porous C catalyst of iron nitrating：
300mg iron chloride and 500mg 2, the stirring of 2 '-bipyridyl are dissolved in ethanol at room temperature, it is above-mentioned then to add 1g
The magnesium oxide template agent being prepared, 12h is stirred, remove solvent, be dried to obtain precursor mixture；
Precursor mixture is placed in tube furnace and under argon gas protection with 10 DEG C/min heating rates to 800 DEG C of calcinings
60 minutes, obtain the composite of template, cementite, iron oxide and the monatomic catalyst of iron；
The template of above-mentioned preparation, cementite, iron oxide and the monatomic catalyst composite of iron are placed in watery hydrochloric acid
Stirring 30min in (0.1mol/L), resulting solid with dilute sulfuric acid (1mol/L) heating boiling reflux 2h, obtain after filtering again
Solid dries 12h, obtains the monatomic porous C catalyst of iron nitrating, is designated as catalyst C, wherein, catalyst C iron content is
1.36wt%, nitrogen content 4.9wt%, specific surface area 914m2/ g, aperture 13.1nm, pore volume 2.99cm3/g。
Embodiment 4
A kind of preparation method of the monatomic porous C catalyst of iron nitrating is present embodiments provided, it comprises the following steps：
The preparation of porous flake hexagon magnesium oxide template agent：
Magnesium oxide powder is scattered in deionized water, and 24h is boiled in backflow, and 80 DEG C are dried overnight, then per minute with 10 DEG C
Heating rate is warming up to 450 DEG C and is calcined 60 minutes, obtains porous flake hexagon magnesium oxide template agent, its specific surface area is
200m2/ g, two-dimensional slice footpath size is about 300nm；
The preparation of the monatomic porous C catalyst of iron nitrating：
300mg ferrous acetates and 500mg 2, the stirring of 2 '-bipyridyl are dissolved in ethanol, then added on 1g at room temperature
The magnesium oxide template agent being prepared is stated, stirs 12h, solvent is removed, is dried to obtain precursor mixture；
Precursor mixture is placed in tube furnace and under argon gas protection with 10 DEG C/min heating rates to 700 DEG C of calcinings
60 minutes, obtain the composite of template, cementite, iron oxide and the monatomic catalyst of iron；Catalyst B iron content
1.83wt%, nitrogen content 6.9wt%, specific surface area 903m2/ g, aperture 10.9nm, pore volume 2.42cm3/g；
The template of above-mentioned preparation, cementite, iron oxide and the monatomic catalyst composite of iron are placed in watery hydrochloric acid
Stirring 30min in (0.1mol/L), resulting solid with dilute sulfuric acid (1mol/L) heating boiling reflux 2h, obtain after filtering again
Solid, 12h is dried, the monatomic porous C catalyst of iron nitrating is obtained, is designated as catalyst D.
Application examples 1
Catalyst A is prepared in the reaction of quinoline applied to 1,2,3,4- tetrahydroquinoline hydroxides, the following institute of concrete operations
Show：23mg catalyst A and the tetrahydroquinolines of 66.6mg (0.5mmol) 1,2,3,4- are well mixed in 2mL acetonitrile solutions, 60
DEG C oxygen atmosphere under after stirring reaction 10h, obtain quinoline, wherein, Fe dosages be 1.8mol% [(23mg × 2.19wt%/
56mg/mmol)/0.5mmol=1.8mol%]；Product is analyzed using GC-MS again, analysis result shows no coupling product
Produce, and catalyst recycle 5 times after activity reduced without obvious.
Application examples 2
The catalyst B that embodiment 2 is obtained is prepared in the reaction of quinoline applied to 1,2,3,4- tetrahydroquinoline dehydrogenation oxidations,
Concrete operations are as follows：By 30mg catalyst B and 66.6mg (0.5mmol) 1,2,3,4- tetrahydroquinolines in 2mL acetonitrile solutions
In be well mixed, under 60 DEG C of oxygen atmosphere after stirring reaction 8h, obtain quinoline, the yield of product quinoline is 97%, TON values
For 47, wherein, Fe dosages are 1.8mol% [(30mg × 1.75wt%/56mg/mmol)/0.5mmol=1.8mol%]；Adopt again
Product is analyzed with GC-MS, analysis result show reaction product in addition to quinoline without other accessory substances produce (see Fig. 8, Fig. 9-
Shown in 14), and catalyst recycle 5 times after activity reduced (as shown in Figure 7) without obvious；
From Fig. 9 and Figure 10 as can be seen that retention time be 4.223 material be internal standard n-dodecane, test spectrogram with
It is consistent to compose library standard spectrogram.
From Figure 11 and Figure 12 as can be seen that retention time be 4.463 material be reaction product quinoline, test spectrogram with
It is consistent to compose library standard spectrogram.
As can be seen that the material that retention time is 4.803 is the tetrahydrochysene quinoline of reaction raw materials 1,2,3,4- from Figure 13 and Figure 14
Quinoline, test spectrogram are consistent with spectrum library standard spectrogram.
Application examples 3
The catalyst C that embodiment 3 is obtained is prepared in the reaction of quinoline applied to 1,2,3,4- tetrahydroquinoline dehydrogenation oxidations,
Concrete operations are as follows：By 36mg catalyst C and 66.6mg (0.5mmol) 1,2,3,4- tetrahydroquinolines in 2mL acetonitrile solutions
In be well mixed, under 60 DEG C of oxygen atmosphere after stirring reaction 12h, obtain quinoline, wherein, Fe dosages are 1.8mol%
[(36mg × 1.37wt%/56mg/mmol)/0.5mmol=1.8mol%], then product is analyzed using GC-MS, analyze
As a result show that no coupling product produces, and catalyst recycle 5 times after activity reduced without obvious.
Application examples 4
The catalyst D that embodiment 4 is obtained is prepared in the reaction of quinoline applied to 1,2,3,4- tetrahydroquinoline dehydrogenation oxidations,
Concrete operations are as follows：By 29mg catalyst and 66.6mg (0.5mmol) 1,2,3,4- tetrahydroquinolines in 2mL acetonitrile solutions
It is well mixed, the stirring reaction 9h under 60 DEG C of oxygen atmosphere, obtain quinoline, wherein, Fe dosages be 1.8mol% [(29mg ×
1.83wt%/56mg/mmol)/0.5mmol=1.8mol%]；Product is analyzed using GC-MS again, analysis result shows
No coupling product produces, and catalyst recycle 5 times after activity reduced without obvious.
Application examples 5
The catalyst B that embodiment 2 is obtained is applied to the fluoro- 1,2,3,4- tetrahydroquinolines dehydrogenation oxidations of 6- and prepares 6- fluorine quinoline
Reaction in, concrete operations are as follows：30mg catalyst B and the 0.5mmol fluoro- 1,2,3,4- tetrahydroquinolines of 6- are existed
It is well mixed in 2mL acetonitrile solutions, the stirring reaction 12h under 60 DEG C of oxygen atmosphere, obtains 6- fluorine quinoline, product 6- fluorine quinoline
Yield be 92%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result shows no pair
Product produces.
Application examples 6
The catalyst B that embodiment 2 is obtained is applied to the chloro- 1,2,3,4- tetrahydroquinolines dehydrogenation oxidations of 6- and prepares 6- chloroquinolines
Reaction in, concrete operations are as follows：30mg catalyst B and the 0.5mmol chloro- 1,2,3,4- tetrahydroquinolines of 6- are existed
It is well mixed in 2mL acetonitrile solutions, the stirring reaction 12h under 60 DEG C of oxygen atmosphere, obtains 6- chloroquinolines, product 6- chloroquinolines
Yield be 98%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result shows no pair
Product produces.
Application examples 7
The catalyst B that embodiment 2 is obtained is applied to the bromo- 1,2,3,4- tetrahydroquinolines dehydrogenation oxidations of 6- and prepares 6- bromoquinolines
Reaction in, concrete operations are as follows：30mg catalyst B and the 0.5mmol bromo- 1,2,3,4- tetrahydroquinolines of 6- are existed
It is well mixed in 2mL acetonitrile solutions, the stirring reaction 12h under 60 DEG C of oxygen atmosphere, obtains 6- bromoquinolines, product 6- bromoquinolines
Yield be 97%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result shows no pair
Product produces.
Application examples 8
The catalyst B that embodiment 2 is obtained is applied to 6- methyl isophthalic acids, and 2,3,4- tetrahydroquinolines dehydrogenation oxidation prepares 6- methyl
In the reaction of quinoline, concrete operations are as follows：By 30mg catalyst B and 0.5mmol 6- methyl isophthalic acids, 2,3,4- tetrahydrochysene quinolines
Quinoline is well mixed in 2mL acetonitrile solutions, the stirring reaction 12h under 60 DEG C of oxygen atmosphere, obtains 6- methylquinolines, product 6-
The yield of methylquinoline is 99%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result
Show that no coupling product produces.
Application examples 9
The catalyst B that embodiment 2 is obtained is applied to 6- methoxyl group -1,2,3,4- tetrahydroquinolines dehydrogenation oxidation and prepares 6- first
In the reaction of phenoxyl quinoline, concrete operations are as follows：By 30mg catalyst B and 0.5mmol 6- methoxyl groups -1,2,3,4-
Tetrahydroquinoline is well mixed in 2mL acetonitrile solutions, the stirring reaction 12h under 60 DEG C of oxygen atmosphere, obtains 6- methoxyl group quinolines
Quinoline, the yield of product 6- methoxy quinolines is 94%.Wherein, Fe dosages are 1.8mol%；Product is divided using GC-MS again
Analysis, analysis result show that no coupling product produces.
Application examples 10
The catalyst B that embodiment 2 is obtained is applied to 6- hydroxyl -1,2,3,4- tetrahydroquinolines dehydrogenation oxidation and prepares 6- hydroxyls
In the reaction of quinoline, concrete operations are as follows：By 30mg catalyst B and 0.5mmol 6- hydroxyl -1,2,3,4- tetrahydrochysene quinolines
Quinoline is well mixed in 2mL acetonitrile solutions, the stirring reaction 12h under 60 DEG C of oxygen atmosphere, obtains 6- oxyquinolines, product 6-
The yield of oxyquinoline is 91%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result
Show that no coupling product produces.
Application examples 11
The catalyst B that embodiment 2 is obtained is applied to 7- hydroxyl -1,2,3,4- tetrahydroquinolines dehydrogenation oxidation and prepares 7- hydroxyls
In the reaction of quinoline, concrete operations are as follows：By 30mg catalyst B and 0.5mmol 7- hydroxyl -1,2,3,4- tetrahydrochysene quinolines
Quinoline is well mixed in 2mL acetonitrile solutions, the stirring reaction 12h under 60 DEG C of oxygen atmosphere, obtains 7- oxyquinolines, product 7-
The yield of oxyquinoline is 94%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result
Show that no coupling product produces.
Application examples 12
The catalyst B that embodiment 2 is obtained is applied to 8- hydroxyl -1,2,3,4- tetrahydroquinolines dehydrogenation oxidation and prepares 8- hydroxyls
In the reaction of quinoline, concrete operations are as follows：By 30mg catalyst B and 0.5mmol 8- hydroxyl -1,2,3,4- tetrahydrochysene quinolines
Quinoline is well mixed in 2mL acetonitrile solutions, the stirring reaction 12h under 60 DEG C of oxygen atmosphere, obtains 8-hydroxyquinoline, product 8-
The yield of oxyquinoline is 85%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result
Show that no coupling product produces.
Application examples 13
The catalyst B that embodiment 2 is obtained is applied to 2- methyl isophthalic acids, and 2,3,4- tetrahydroquinolines dehydrogenation oxidation prepares 2- methyl
In the reaction of quinoline, concrete operations are as follows：By 30mg catalyst B and 0.5mmol 2- methyl isophthalic acids, 2,3,4- tetrahydrochysene quinolines
Quinoline is well mixed in 2mL acetonitrile solutions, the stirring reaction 12h under 60 DEG C of oxygen atmosphere, obtains 2- methylquinolines, product 2-
The yield of methylquinoline is 69%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result
Show that no coupling product produces.
Application examples 14
The catalyst B that embodiment 2 is obtained is applied to 6- nitro -1,2,3,4- tetrahydroquinolines dehydrogenation oxidation and prepares 6- nitros
In the reaction of quinoline, concrete operations are as follows：By 30mg catalyst B and 0.5mmol 6- nitro -1,2,3,4- tetrahydrochysene quinolines
Quinoline is well mixed in 2mL acetonitrile solutions, the stirring reaction 18h under 60 DEG C of oxygen atmosphere, obtains 6- nitroquinolines, product 6-
The yield of nitroquinoline is 95%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result
Show that no coupling product produces.
Application examples 15
The catalyst B that embodiment 2 is obtained is applied to 6- carboxyl -1,2,3,4- tetrahydroquinolines dehydrogenation oxidation and prepares 6- carboxyls
In the reaction of quinoline, concrete operations are as follows：By 30mg catalyst B and 0.5mmol 6- carboxyl -1,2,3,4- tetrahydrochysene quinolines
Quinoline is well mixed in 2mL acetonitrile solutions, the stirring reaction 18h under 60 DEG C of oxygen atmosphere, obtains 6- carboxyl quinolines, product 6-
The yield of carboxyl quinoline is 93%.Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result
Show that no coupling product produces.
Application examples 16
The catalyst B that embodiment 2 obtains is prepared into the anti-of isoquinolin applied to 1,2,3,4- tetrahydroisoquinoline dehydrogenation oxidations
Ying Zhong, concrete operations are as follows：30mg catalyst B and 0.5mmol 1,2,3,4- tetrahydroisoquinolines is molten in 2mL acetonitriles
It is well mixed in liquid, the stirring reaction 18h under 60 DEG C of oxygen atmosphere, obtains isoquinolin, the yield of product isoquinolin is 86%.
Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result shows that no coupling product produces.
Application examples 17
The catalyst B that embodiment 2 obtains is prepared into the anti-of quinoxaline applied to 1,2,3,4- tetrahydroquinoxaline dehydrogenation oxidations
Ying Zhong, concrete operations are as follows：30mg catalyst B and 0.5mmol 1,2,3,4- tetrahydroquinoxalines is molten in 2mL acetonitriles
It is well mixed in liquid, the stirring reaction 18h under 60 DEG C of oxygen atmosphere, obtains quinoxaline, the yield of product quinoxaline is 80%.
Wherein, Fe dosages are 1.8mol%；Product is analyzed using GC-MS again, analysis result shows that no coupling product produces.
Comparative example
Experimental data in the document 1-8 that will be mentioned in experimental data and background technology in the application application examples 2 is carried out
Contrast, concrete outcome refers to as shown in table 1 below：
Table 1
From table 1 it follows that in the catalyst reacted for being catalyzed nitrogen-containing heterocycle compound dehydrogenation oxidation, noble metal
The TON values of catalyst are higher, but its severe reaction conditions, and by comparison, the monatomic iron nitrating provided using the application is more
Reaction temperature and time can be greatly reduced in hole C catalyst catalysis nitrogen-containing heterocycle compound dehydrogenation oxidation reaction；It is and existing non-expensive
The TON values of metal-based catalysts are relatively low, by comparison, the TON values for the monatomic porous C catalyst of iron nitrating that the application provides
It is higher, it can be seen that, the monatomic porous C catalyst of iron nitrating that the application provides has excellent catalysis nitrogen heterocyclic ring chemical combination
The performance of thing dehydrogenation oxidation reaction.
Claims (10)
- A kind of 1. monatomic porous C catalyst of iron nitrating, it is characterised in that the catalyst using monatomic iron as active component, with Nitrating porous carbon materials are carrier, and iron is scattered in nitrating porous carbon materials carrier surface and inside with monatomic form, wherein, Counted using the gross weight of the monatomic porous C catalyst of iron nitrating as 100%, it contains 1.0-3.0wt% iron and 4.0- 9.0wt% nitrogen.
- 2. the monatomic porous C catalyst of iron nitrating according to claim 1, it is characterised in that the ratio surface of the catalyst Product is 800-1000m2/ g, aperture 10-14nm, pore volume 2-4cm3/g。
- 3. the preparation method of the monatomic porous C catalyst of iron nitrating described in claim 1 or 2, it comprises the following steps：(1) molysite, nitrogenous organic ligand and template are well mixed in a solvent, then remove solvent, be dried to obtain one Solid mixture；Preferably, the mass ratio of the molysite, nitrogenous organic ligand and template is 1:0.5-4:1.5-6；(2) solid mixture is calcined 0.5-4 hours at 600-1000 DEG C, obtain composite；It is further preferred that the calcining is carried out under inert gas shielding, the inert gas includes argon gas and/or nitrogen；It is further preferred that solid mixture temperature is risen to by 600- from room temperature with 5-25 DEG C/min heating rate in step (2) 1000℃；(3) acid treatment is carried out to the composite, obtains the monatomic porous C catalyst of iron nitrating；It is further preferred that the acid treatment specifically includes following steps：The composite is handled using watery hydrochloric acid first To remove template, then dilute sulfuric acid is used in a heated condition to be handled products therefrom after watery hydrochloric acid processing to remove impurity Particle.
- 4. the preparation method of the monatomic porous C catalyst of iron nitrating according to claim 3, it is characterised in that the mould Plate agent includes porous flake hexagon magnesia；Preferably, the specific surface area of the porous flake hexagon magnesia is 100- 300m2/ g, two-dimensional slice footpath size are 200-400nm；It is highly preferred that the porous flake hexagon magnesia is by following step Suddenly it is prepared：Magnesium oxide powder is boiled in water and kept for 12-72 hours, by obtained solid after drying, then 400-800 DEG C of calcining 1-4 hour, obtain described porous flake hexagon magnesia；It is further preferred that the solid is through dry After dry, temperature is risen to 400-800 DEG C from room temperature with 5-25 DEG C/min heating rate.
- 5. the preparation method of the monatomic porous C catalyst of iron nitrating according to claim 3, it is characterised in that the iron Salt includes one or more of combinations in ferric sulfate, ferric nitrate, iron chloride and ferrous acetate.
- 6. the preparation method of the monatomic porous C catalyst of iron nitrating according to claim 3, it is characterised in that described to contain Nitrogen organic ligand includes 2,2'- bipyridyls, pyridine, phenanthrolene, 2,2':6', 2 "-ter cycloheptapyridine, (the 2- benzo miaows of 2,6- bis- Oxazolyl) one or more of combinations in pyridine and pyrroles.
- 7. the preparation method of the monatomic porous C catalyst of iron nitrating according to claim 3, it is characterised in that step (1) solvent described in includes one or more of combinations in ethanol, water, acetone and ethyl acetate.
- 8. a kind of monatomic iron nitrating porous carbon catalyst nitrogen-containing heterocycle compound using described in claim 1 or 2 takes off The method of hydroxide reaction, this method comprise the following steps：The catalyst is well mixed in a solvent with nitrogen-containing heterocycle compound, and in stirring bar under oxygen or air atmosphere Dehydrogenation oxidation reaction is carried out under part；Wherein it is preferred to the mass ratio of the catalyst and nitrogen-containing heterocycle compound is 1:1.5-4.0 catalyst and solvent Mass ratio is 0.01-0.03:1；It is further preferred that the solvent includes one kind in acetonitrile, ethanol, ethyl acetate, toluene, acetone, hexamethylene and normal heptane Several combination of meeting；It is further preferred that reaction temperature is 40-80 DEG C, the reaction time is 5-18 hours.
- 9. according to the method for claim 8, it is characterised in that the nitrogen-containing heterocycle compound includes 1,2,3,4- tetrahydrochysene quinolines Appointing in quinoline and its derivative, 1,2,3,4- tetrahydroisoquinolines and its derivative or 1,2,3,4- tetrahydroquinoxalines and its derivative It is a kind of；Preferably, described 1, the derivative of 2,3,4- tetrahydroquinolines includes methyl, hydroxyl, methoxyl group, halogen, nitro and carboxyl point Not in the 1,2,3,4- tetrahydroquinolines of 5,6,7, No. 8 position substitutions；It is further preferred that described 1, the derivative of 2,3,4- tetrahydroisoquinolines includes methyl, hydroxyl, methoxyl group, halogen, nitro and carboxylic Base is respectively in the 1,2,3,4- tetrahydroisoquinolines of 5,6,7, No. 8 position substitutions；It is further preferred that described 1, the derivative of 2,3,4- tetrahydroquinoxalines includes methyl, hydroxyl, methoxyl group, halogen, nitro and carboxylic Base is respectively in the 1,2,3,4- tetrahydroquinoxalines of 5,6,7, No. 8 position substitutions.
- 10. the monatomic porous C catalyst of iron nitrating described in claim 1 or 2 is in catalysis nitrogen-containing heterocycle compound dehydrogenation oxidation Application in reaction.
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