CN108339562A - A kind of preparation method and products obtained therefrom of the azotized carbon nano pipe of iron ion doping - Google Patents
A kind of preparation method and products obtained therefrom of the azotized carbon nano pipe of iron ion doping Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 34
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 150000002505 iron Chemical class 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 iron ion Chemical class 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 18
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 13
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 239000002071 nanotube Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000010792 warming Methods 0.000 abstract 1
- 229920000877 Melamine resin Polymers 0.000 description 38
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 32
- 238000000034 method Methods 0.000 description 22
- 238000001816 cooling Methods 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 14
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 13
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 150000007974 melamines Chemical class 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 230000019552 anatomical structure morphogenesis Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/61—
Abstract
The invention discloses the preparation method and products obtained therefrom of a kind of azotized carbon nano pipe of iron ion doping, step is：Nitrogenous organic precursor, trivalent iron salt and water are made into homogeneous solution, is warming up to after boiling and carries out decrease temperature crystalline according to specific rate of temperature fall, gained crystal calcines to obtain final products.The present invention realizes the Uniform Doped of iron ion using crystal from crystallization, preparation process is simple, yield is high, products obtained therefrom is nanotube-shaped, and wall thickness is 3 20 nanometers, the nanotube large specific surface area of this thin-walled, with high reactivity, iron ion is distributed in the piperazine loop network of C3N4, will not be oxidized, and has important application in field of energy source materials.
Description
Technical field
The present invention relates to a kind of preparation methods of ion doping type carbonitride, and in particular to a kind of nitridation of iron ion doping
The preparation method and products obtained therefrom of carbon nanotube, belong to technical field of semiconductor material preparation.
Background technology
Carbonitride is nontoxic as one kind, be easily-synthesized, physicochemical properties are stable, have compared with low energy gap（Band gap is about 2.7
ev）And the organic semiconductor that earth content is high, the extensive concern of people was caused in recent years.The carbonitride of graphite-phase is due to tool
There is the layer structure of class graphene, and there are a series of properties similar with graphene, thus people have carried out it largely
Exploration, be applied to the numerous areas such as photocatalytic degradation, Photocatalyzed Hydrogen Production, analytical chemistry.
For carbonitride, it is to improve photo-generated carrier separation transfer to increase carbonitride active site and ion doping
Effective means.The work for carrying out ion doping at present has very much, but the method that everybody generally uses is by nitrogenous organosilane precursor
Body（Such as melamine, dicyandiamide, thiocarbamide）Grinding early period is carried out with related salts, by pyrocondensation collecting process, synthesis ion is mixed
Miscellaneous type carbonitride.But these method resulting product patterns are bulk, most size is larger, and specific surface area is smaller, and grinds
The product intermediate ion doping for calcining formation afterwards is uneven, because easily being diffused to the surface in thermal polycondensation process intermediate ion, carbonitride
The ion on surface is easy oxidation.Therefore, a kind of new ion doping method of searching is unevenly distributed with solving Doped ions, is adulterated
The problem that ion is oxidizable, product size is big, specific surface area is small is great researching value.
In addition, the pattern of carbon nitride material is to its performance also important.Nanotube pattern, which is made, in carbonitride is
Its Photocatalyzed Hydrogen Production, the effective means of a series of performance such as photocatalytic degradation organic matter are improved, but has no simple, conveniently at present
Ion doping type azotized carbon nano pipe relevant report.
Invention content
It is uneven for ion doping present in existing ion doping type carbonitride preparation process, Doped ions are oxidizable
The deficiencies of, the present invention provides the preparation method and products obtained therefrom of a kind of azotized carbon nano pipe of iron ion doping, this method behaviour
It is simple to make process, reproducible, controllability is good, and gained graphite phase carbon nitride is nanotube pattern, and iron ion is evenly distributed, is not easy
Oxidation.
Specific technical solution of the present invention is as follows：
A kind of preparation method of the azotized carbon nano pipe of iron ion doping, this approach includes the following steps：
（1）Nitrogenous organic precursor, trivalent iron salt and water are made into homogeneous solution；
（2）By step（1）Homogeneous solution be heated to boiling, be then down to room temperature according to the rate of temperature fall of 1-5 DEG C/min, into
Row crystallization；
（3）The crystal of precipitation is calcined, the azotized carbon nano pipe of iron ion doping is obtained.
The present invention realizes the formation of the Uniform Doped of iron ion and the pattern of nanotube by crystallizing and calcining two processes.
First, the solution of nitrogenous organic precursor, trivalent iron salt and water composition is prepared, nitrogenous organic precursor is in supersaturation in the solution
State is cooled down the supersaturated solution after being heated to boiling according to special rate of temperature fall stage by stage, it is nitrogenous it is organic before
Drive body crystal can be gradually precipitated during cooling, while during crystallization iron ion can adulterate into it is nitrogenous it is organic before
It drives in body crystal.In subsequent calcination process, pass through high temperature thermal polycondensation doped with the nitrogenous organic precursor crystal of iron ion
Effect forms nanotube pattern.During thermal polycondensation, iron ion and C3N4In nitrogen formed coordinate bond, be fixed on C3N4Piperazine
In loop network, do not diffuse to the surface.The presence of iron ion plays facilitation, iron to the generation of the tubular looks of azotized carbon nano
Ion stabilized presence is in C3N4It in piperazine loop network, will not be oxidized, and be evenly distributed.
Further, step（1）In, when preparing homogeneous solution, the dissolving of nitrogenous organic precursor, is adding for convenience
It is dissolved in water in the case of heat, stirring.For example, can first mix nitrogenous organic precursor with water, it is heated to flowing back,
It is completely dissolved to nitrogenous organic precursor, trivalent iron salt is then added and is uniformly mixed.The trivalent iron salt is with solid or aqueous solution
Form be added.
Further, step（1）The composition of homogeneous solution, temperature-fall period for ion doping and product morphogenesis
It has a major impact.Preferably, in the homogeneous solution of nitrogenous organic precursor, trivalent iron salt and water, nitrogenous organic precursor it is dense
Degree is 20-40g/L.Preferably, the mass ratio of nitrogenous organic precursor and trivalent iron salt is 100:0.1-1.
Further, step（2）In, the homogeneous solution of heating is down to room temperature according to the rate of temperature fall of 1-5 DEG C/min,
Carry out crystallization.
Further, the nitrogenous organic precursor be melamine or dicyandiamide, the trivalent iron salt be iron chloride or
Ferric nitrate.
Further, step（3）In, calcination temperature is 550-650 DEG C, calcination time 2-6h.Preferably, according to 2-5
DEG C/heating rate of min rises to 550-650 DEG C and calcined.
Further, step（3）In, calcining carries out under gas shield, and the gas is preferably nitrogen or inert gas.
The azotized carbon nano pipe outside diameter of iron ion doping obtained by the method for the present invention is 200-800 nanometers, and wall thickness is received for 3-20
Rice.The length of nanotube is generally 3-5 microns.This nanometer of tube wall is thin, and soft fluffy state is presented in tube wall.The pattern and conventional method
Bulk morphologies obtained theoretically have higher specific surface area, and performance is more preferably.Products obtained therefrom of the present invention is also protected in the present invention
Within the scope of.
Further, it in the azotized carbon nano pipe of present invention gained iron ion doping, is verified through XRD diffraction spectras, XRD diffraction
Occur in spectrum with the relevant characteristic peak of ferro element, therefore show that state of the iron really with ferric ion in nanotube is deposited
.This side demonstrates iron ion during preparation and forms coordinate bond with the N in carbonitride, is fixed on C3N4Piperazine ring
In network.
In aqueous environment, using the Uniform Doped for gradually realizing iron ion from crystallization of crystal, iron has been made in the present invention
The azotized carbon nano pipe of ion doping, this method is simple and easy to do, reproducible, and yield is high, and gained iron ion is uniformly distributed in
It in graphite phase carbon nitride piperazine loop network, will not be oxidized, efficiently avoid that iron ion is oxidizable, the problem of being unevenly distributed.
The azotized carbon nano tube wall for the iron ion doping that the present invention synthesizes is thin, and nanotube is in soft fluffy state, this satisfaction
People are to the exploration demand in terms of carbonitride pattern improvement.Pattern of the present invention is than traditional bulk morphologies large specific surface area, tool
There is higher reactivity, is conducive to the separation for further increasing photo-generate electron-hole pair and transfer, it is organic in photocatalytic degradation
The great application prospect in the fields such as object, Photocatalyzed Hydrogen Production, energy and material, analytical chemistry.
Description of the drawings
The scanning electron microscope of 1 products obtained therefrom of Fig. 1 embodiment of the present invention（SEM）Photo.
X-ray diffraction (XRD) collection of illustrative plates of 1 products obtained therefrom of Fig. 2 embodiment of the present invention.
The scanning electron microscope of 2 products obtained therefrom of Fig. 3 embodiment of the present invention（SEM）Photo.
The scanning electron microscope of Fig. 41 products obtained therefroms of comparative example of the present invention（SEM）Photo.
The scanning electron microscope of Fig. 52 melamine of comparative example calcining products obtained therefroms of the present invention（SEM）Photo.
The scanning electron microscope of Fig. 62 dicyandiamide of comparative example calcining products obtained therefroms of the present invention（SEM）Photo.
The scanning electron microscope of Fig. 73 products obtained therefroms of comparative example of the present invention（SEM）Photo.
The scanning electron microscope of Fig. 84 products obtained therefroms of comparative example of the present invention（SEM）Photo.
The scanning electron microscope of Fig. 95 products obtained therefroms of comparative example of the present invention（SEM）Photo.
Specific implementation mode
Below by embodiment, the present invention will be further elaborated, it should be appreciated that, following the description merely to
It explains the present invention, its content is not defined.
Embodiment 1
1.1 flow back 2 g melamines and 100 ml deionized waters at 100 DEG C, until melamine is completely dissolved, obtain
Melamine aqueous solution.
1.2 are made into anhydrous ferric chloride the ferric chloride in aqueous solution of a concentration of 0.02 g/ml, and 100 microlitres of iron chloride are water-soluble
Liquid be added melamine aqueous solution in, under stiring, 100 DEG C reflux 30 min, so that melamine and iron chloride is sufficiently mixed
It is even.
1.3 are cooled down above-mentioned 1.2 solution stage by stage, and concrete operations are：Above-mentioned 1.2 100 DEG C of solution is pressed
Cool down according to the rate of temperature fall of 1 DEG C/min, until being down to room temperature, there is crystal to be gradually precipitated during cooling.
1.4 after crystallization is complete, and the crystal of precipitation is taken out from solution, and the solution on crystal is blotted on filter paper, is obtained
To the melamine crystals of Fe2O3 doping.
1.5 by the melamine crystals of Fe2O3 doping obtained above argon gas protection under, with the liter of 2 DEG C/min
Warm speed is heated to 550 DEG C, and keeps the temperature 4 h, later with stove natural cooling.
1.6, by the sample mortar grinder after calcining, obtain final products.
Fig. 1 is the stereoscan photograph of products obtained therefrom, it can be seen from the figure that products obtained therefrom is in nanotube-shaped, nanotube
Size is 3-5 microns, and outer diameter is 200-800 nanometers, and pipe thickness is 3-20 nanometers, and nanotube shows soft fluffy state.Through BET
Test, specific surface area are 87.9 m2/g。
Fig. 2 is the X ray diffracting spectrum of product, and 13.1 ° of graphite phase carbon nitride and 27.4 ° of spy are only shown in collection of illustrative plates
Peak is levied, does not occur and is deposited by coordinate bond with the relevant characteristic peak of iron it is possible thereby to which side proves that iron exists with ionic condition
In C3N4In piperazine loop network.
Embodiment 2
2.1 flow back 2 g melamines and 100 ml deionized waters at 100 DEG C, until melamine is completely dissolved, obtain
Melamine aqueous solution.
2.2 are made into anhydrous ferric chloride the ferric chloride in aqueous solution of a concentration of 0.02 g/ml, and 500 microlitres of iron chloride are water-soluble
Liquid be added melamine aqueous solution in, under stiring, 100 DEG C reflux 30 min, so that melamine and iron chloride is sufficiently mixed
It is even.
2.3 are cooled down above-mentioned 2.2 solution stage by stage, and concrete operations are：Above-mentioned 2.2 100 DEG C of solution is pressed
Cool down according to the rate of temperature fall of 1 DEG C/min, until being down to room temperature, there is crystal to be gradually precipitated during cooling.
2.4 after crystallization is complete, and the crystal of precipitation is taken out from solution, and the solution on crystal is blotted on filter paper, is obtained
To the melamine crystals of Fe2O3 doping.
2.5 by the melamine crystals of Fe2O3 doping obtained above argon gas protection under, with the liter of 2 DEG C/min
Warm speed is heated to 550 DEG C, and keeps the temperature 4 h, later with stove natural cooling.
2.6, by the sample mortar grinder after calcining, obtain the azotized carbon nano pipe of iron ion doping.
Fig. 3 is the SEM photograph of products obtained therefrom, it can be seen from the figure that the nanotube that products obtained therefrom is 3-5 microns, nanometer
Pipe is in soft fluffy state, and outer diameter is 200-800 nanometers, and wall thickness is 10-20 nanometers.It is tested through BET, specific surface area is 86.2 m2/
g.It is verified through X ray diffracting spectrum, product is graphite phase carbon nitride, and iron exists with ionic condition in C3N4In piperazine loop network.
Embodiment 3
3.1 flow back 2 g melamines and 100 ml deionized waters at 100 DEG C, until melamine is completely dissolved, obtain
Melamine aqueous solution.
3.2 are made into anhydrous ferric chloride the ferric chloride in aqueous solution of a concentration of 0.02 g/ml, by 1 milliliter of ferric chloride in aqueous solution
Be added melamine aqueous solution in, under stiring, 100 DEG C reflux 30 min, so that melamine and iron chloride is sufficiently mixed uniformly.
3.3 are cooled down above-mentioned 3.2 solution stage by stage, and concrete operations are：Above-mentioned 3.2 100 DEG C of solution is pressed
Cool down according to the rate of temperature fall of 1 DEG C/min, until being down to room temperature, there is crystal to be gradually precipitated during cooling.
3.4 after crystallization is complete, and the crystal of precipitation is taken out from solution, and the solution on crystal is blotted on filter paper, is obtained
To the melamine crystals of Fe2O3 doping.
3.5 by the melamine crystals of Fe2O3 doping obtained above argon gas protection under, with the liter of 2 DEG C/min
Warm speed is heated to 550 DEG C, and keeps the temperature 4 h, later with stove natural cooling.
3.6, by the sample mortar grinder after calcining, obtain the azotized carbon nano pipe of iron ion doping.Azotized carbon nano
Pipe is in soft fluffy state, and size is 3-5 microns, and outer diameter is 200-800 nanometers, and wall thickness is 13-20 nanometers.It is tested through BET, compares table
Area is 85.5 m2/g.It is verified through X ray diffracting spectrum, product is graphite phase carbon nitride, and iron exists with ionic condition in C3N4
In piperazine loop network.
Embodiment 4
4.1 flow back 4g dicyandiamides and 100 ml deionized waters at 100 DEG C, until dicyandiamide is completely dissolved, obtain dicyandiamide
Aqueous solution.
4.2 are made into anhydrous ferric chloride the ferric chloride in aqueous solution of a concentration of 0.02 g/ml, and 200 microlitres of iron chloride are water-soluble
Liquid be added dicyandiamide aqueous solution in, under stiring, 100 DEG C reflux 30 min, so that dicyandiamide and iron chloride is sufficiently mixed uniformly.
4.3 are cooled down above-mentioned 4.2 solution stage by stage, and concrete operations are：Above-mentioned 4.2 100 DEG C of solution is pressed
Cool down according to the rate of temperature fall of 1 DEG C/min, until being down to room temperature, there is crystal to be gradually precipitated during cooling.
4.4 after crystallization is complete, and the crystal of precipitation is taken out from solution, and the solution on crystal is blotted on filter paper, is obtained
To the dicyandiamide crystal of Fe2O3 doping.
4.5 by the dicyandiamide crystal of Fe2O3 doping obtained above argon gas protection under, with the heating of 2 DEG C/min
Speed is heated to 550 DEG C, and keeps the temperature 4 h, later with stove natural cooling.
4.6, by the sample mortar grinder after calcining, obtain the azotized carbon nano pipe of iron ion doping.Products obtained therefrom shape
Looks are substantially similar to Example 1, and nanotube is in soft fluffy state, and size is 3-5 microns, and outer diameter is 300-700 nanometers, wall thickness 3-
20 nanometers.It is tested through BET, specific surface area is 85.3 m2/g.It is verified through X ray diffracting spectrum, product nitrogenizes for graphite-phase
Carbon, iron exist with ionic condition in C3N4In piperazine loop network.
Embodiment 5
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 1, unlike：Iron chloride is changed to nitric acid
Iron.The tubular looks of azotized carbon nano of gained iron ion doping are similar to Example 1, and to be fluffy nanotube-shaped, size is that 3-5 is micro-
Rice, outer diameter are 300-800 nanometers, and wall thickness is 5-20 nanometers.It is tested through BET, specific surface area is 85.5 m2/g.Spread out through X-ray
Collection of illustrative plates verification is penetrated, product is graphite phase carbon nitride, and iron exists with ionic condition in C3N4In piperazine loop network.
Embodiment 6
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 2, unlike：According to the cooling of 3 DEG C/min
Rate cools down.The azotized carbon nano pipe of gained iron ion doping is in puffy, and size is 3-5 microns, outer diameter 200-800
Nanometer, wall thickness are 3-20 nanometers.It is tested through BET, specific surface area is 86.1 m2/g.It is verified through X ray diffracting spectrum, product
For graphite phase carbon nitride, iron exists with ionic condition in C3N4In piperazine loop network.
Embodiment 7
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 3, unlike：According to the cooling of 2 DEG C/min
Rate cools down.The azotized carbon nano pipe of gained iron ion doping is in puffy, and size is 3 ~ 5 microns, outer diameter 200-800
Nanometer, wall thickness are 3-20 nanometers.It is tested through BET, specific surface area is 87.1 m2/g.It is verified through X ray diffracting spectrum, product
For graphite phase carbon nitride, iron exists with ionic condition in C3N4In piperazine loop network.
Embodiment 8
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 1, unlike：According to the cooling of 5 DEG C/min
Rate cools down.The azotized carbon nano pipe of gained iron ion doping is in puffy, and size is 3-4 microns, outer diameter 200-800
Nanometer, wall thickness are 3-20 nanometers.It is tested through BET, specific surface area is 86.4 m2/g.It is verified through X ray diffracting spectrum, product
For graphite phase carbon nitride, iron exists with ionic condition in C3N4In piperazine loop network.
Embodiment 9
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 1, unlike：When calcining, with 5 DEG C/min
Heating rate be heated to 550 DEG C, and 4 h are kept the temperature, later with stove natural cooling.The azotized carbon nano of gained iron ion doping
Pipe is in puffy, and size is 3-5 microns, and outer diameter is 200-800 nanometers, and wall thickness is 10-20 nanometers.It is tested through BET, specific surface
Product is 85.5 m2/g.It is verified through X ray diffracting spectrum, product is graphite phase carbon nitride, and iron exists with ionic condition in C3N4Piperazine
In loop network.
Embodiment 10
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 1, unlike：Calcination temperature is 600 DEG C.
The azotized carbon nano pipe of gained iron ion doping is in puffy, and size is 3-5 microns, and outer diameter is 200-800 nanometers, wall thickness 5-
15 nanometers.It is tested through BET, specific surface area is 86.7 m2/g.It is verified through X ray diffracting spectrum, product nitrogenizes for graphite-phase
Carbon, iron exist with ionic condition in C3N4In piperazine loop network.
Embodiment 11
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 1, unlike：Calcination temperature is 650 DEG C.
The azotized carbon nano pipe of gained iron ion doping is in puffy, and size is 3-5 microns, and outer diameter is 200-800 nanometers, wall thickness 3-
10 nanometers.It is tested through BET, specific surface area is 87.7 m2/g.It is verified through X ray diffracting spectrum, product nitrogenizes for graphite-phase
Carbon, iron exist with ionic condition in C3N4In piperazine loop network.
Embodiment 12
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 1, unlike：Calcination time is 2h.Gained
The azotized carbon nano pipe of iron ion doping is in puffy, and size is 3-5 microns, and outer diameter is 200-800 nanometers, wall thickness 15-20
Nanometer.It is tested through BET, specific surface area is 83.6 m2/g.It is verified through X ray diffracting spectrum, product is graphite phase carbon nitride,
Iron exists with ionic condition in C3N4In piperazine loop network.
Embodiment 13
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 1, unlike：Calcination time is 6h.Gained
The azotized carbon nano pipe of iron ion doping is in puffy, and size is 3-5 microns, and outer diameter is 200-800 nanometers, and wall thickness is received for 3-12
Rice.It is tested through BET, specific surface area is 86.2 m2/g.It is verified through X ray diffracting spectrum, product is graphite phase carbon nitride, iron
Exist in C with ionic condition3N4In piperazine loop network.
Comparative example 1
1.1 prepare melamine aqueous solution, with embodiment 1.
1.2 are made into anhydrous ferric chloride the ferric chloride in aqueous solution of a concentration of 0.02 g/ml, and 100 microlitres of iron chloride are water-soluble
Liquid be added melamine aqueous solution in, under stiring, 100 DEG C reflux 30 min.
1.3 are cooled down above-mentioned 1.2 solution stage by stage, specially：Often cool down 10 DEG C, 10 min of insulated and stirred, directly
To being down to room temperature.
1.4 by the melamine crystals naturally dry of precipitation, with the heating speed of 2 DEG C/min under argon gas protection
Degree is heated to 550 DEG C, and keeps the temperature 4 h, later with stove natural cooling.
1.5, by the sample mortar grinder after calcining, obtain product.
Fig. 4 is the stereoscan photograph of products obtained therefrom.By photo as can be seen that products obtained therefrom is sheet-like morphology.
Comparative example 2
2.1 flow back 2 g melamines or dicyandiamide and 100 ml deionized waters at 100 DEG C, until melamine or double
Cyanamide is completely dissolved.
2.2 are cooled down above-mentioned 2.1 solution stage by stage, and concrete operations are：Above-mentioned 2.1 100 DEG C of solution is pressed
Cool down according to the rate of temperature fall of 1 DEG C/min, until being down to room temperature, there is crystal to be gradually precipitated during cooling.
2.3 after crystallization is complete, and the crystal of precipitation is taken out from solution, and the solution on crystal is blotted on filter paper；
2.4 by the crystal of precipitation under argon gas protection, be heated to 550 DEG C with the heating rate of 2 DEG C/min, and keep the temperature 4
H, later with stove natural cooling.
The 2.5 sample mortar grinders for obtaining calcining, obtain final products.
Fig. 5 is the stereoscan photograph of melamine calcining products obtained therefrom, by photo as can be seen that product is blocky shape
Looks do not have tubular morphology appearance in the visual field.Fig. 6 is the stereoscan photograph of dicyandiamide calcining products obtained therefrom, can by photo
To find out, product also shows as bulk morphologies, does not have tubular morphology appearance in the visual field.
Comparative example 3
The carbonitride of iron ion doping is prepared according to the method for embodiment 1, unlike：Melamine is changed to thiocarbamide.Gained
The SEM of product schemes as shown in fig. 7, product is the thin slice pattern of curling, does not have tubular morphology appearance in the visual field.
Comparative example 4
4.1 flow back 2 g melamines and 100 ml deionized waters at 100 DEG C, until melamine is completely dissolved, obtain
Melamine aqueous solution.
4.2 are made into anhydrous ferric chloride the ferric chloride in aqueous solution of a concentration of 0.02 g/ml, and 100 microlitres of iron chloride are water-soluble
Liquid be added melamine aqueous solution in, under stiring, 100 DEG C reflux 30 min.
Above-mentioned 4.2 solution is down to room temperature by 4.3 naturally.
4.4 by the melamine crystals naturally dry of precipitation, with the heating speed of 2 DEG C/min under argon gas protection
Degree is heated to 550 DEG C, and keeps the temperature 4 h, later with stove natural cooling.
The 4.5 sample mortar grinders for obtaining calcining, obtain final products.
Fig. 8 is the stereoscan photograph of products obtained therefrom.By photo as can be seen that products obtained therefrom is packed together for thin slice
Bulk morphologies, do not have tubular morphology appearance in the visual field.
Comparative example 5
5.1 grind 2 g melamines and 0.02 g iron chloride uniformly in mortar.
5.2 are mixed with ferric melamine under argon gas protection by obtained above, with 2 DEG C/min's
Heating rate is heated to 550 DEG C, and keeps the temperature 4 h, later with stove natural cooling.
The 5.3 sample mortar grinders for obtaining step 5.2, obtain final products.
Fig. 9 is the stereoscan photograph of products obtained therefrom, and pattern is foam-like.Meanwhile product is provided with magnetism, part three
Valence iron ion has been oxidized to the di-iron trioxide of γ phases.
Comparative example 6
The azotized carbon nano pipe of iron ion doping is prepared according to the method for embodiment 1, unlike：With the heating of 10 DEG C/min
Speed is heated to 550 DEG C, and keeps the temperature 4 h, later with stove natural cooling.Products obtained therefrom is sheet.
Claims (10)
1. the preparation method of the azotized carbon nano pipe of a kind of iron ion doping, it is characterized in that including the following steps：
（1）Nitrogenous organic precursor, trivalent iron salt and water are made into homogeneous solution；
（2）By step（1）Homogeneous solution ebuillition of heated, be then down to room temperature according to the rate of temperature fall of 1-5 DEG C/min, carry out
Crystallization；
（3）The crystal of precipitation is calcined, the azotized carbon nano pipe of iron ion doping is obtained.
2. preparation method according to claim 1, it is characterized in that：Nitrogenous organic precursor, trivalent iron salt and water it is uniform
In solution, a concentration of 20-40 g/L of nitrogenous organic precursor.
3. preparation method according to claim 1 or 2, it is characterized in that：The quality of nitrogenous organic precursor and trivalent iron salt
Than being 100:0.1-1.
4. preparation method according to any one of claim 1-3, it is characterized in that：Step（1）When middle preparation homogeneous solution,
Nitrogenous organic precursor is mixed with water first, is heated to flowing back, until nitrogenous organic precursor is completely dissolved, ferric iron is then added
Salt is uniformly mixed, and the trivalent iron salt is added in the form of solid or aqueous solution.
5. according to the preparation method described in any one of claim 1-4, it is characterized in that：The nitrogenous organic precursor is trimerization
Cyanamide or dicyandiamide, the trivalent iron salt are iron chloride or ferric nitrate.
6. preparation method according to claim 1, it is characterized in that：Step（3）In, calcination temperature is 550-650 DEG C, is forged
The burning time is 2-6 h.
7. preparation method according to claim 1 or 6, it is characterized in that：Step（3）In, with the heating speed of 2-5 DEG C/min
Degree rises to 550-650 DEG C and is calcined.
8. preparation method according to claim 1 or 6, it is characterized in that：Step（3）In, calcining carries out under gas shield,
The gas is preferably nitrogen or inert gas.
9. according to the preparation method described in any one of claim 1-8, it is characterized in that：The carbonitride of gained iron ion doping is received
The outer diameter of mitron is 200-800 nanometers, and wall thickness is 3-20 nanometers；Iron is evenly distributed on C with trivalent ion state3N4Piperazine loop network
In.
10. made from the preparation method according to the azotized carbon nano pipe of the iron ion doping described in any one of claim 1-9
The azotized carbon nano pipe of iron ion doping.
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