CN108339562B - Preparation method of iron ion doped carbon nitride nanotube and obtained product - Google Patents
Preparation method of iron ion doped carbon nitride nanotube and obtained product Download PDFInfo
- Publication number
- CN108339562B CN108339562B CN201810140017.5A CN201810140017A CN108339562B CN 108339562 B CN108339562 B CN 108339562B CN 201810140017 A CN201810140017 A CN 201810140017A CN 108339562 B CN108339562 B CN 108339562B
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- iron
- nitrogen
- doped carbon
- containing organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 98
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 66
- 239000002071 nanotube Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 34
- -1 iron ion Chemical class 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 40
- 229920000877 Melamine resin Polymers 0.000 claims description 39
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 37
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 26
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 26
- 150000002500 ions Chemical class 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 21
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- 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 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 239000006104 solid solution Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 53
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 239000012467 final product Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 13
- 239000010439 graphite Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000227 grinding Methods 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 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
- 238000001228 spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Images
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 a preparation method of iron ion doped carbon nitride nanotubes and an obtained product, and the preparation method comprises the following steps: preparing a nitrogen-containing organic precursor, a ferric iron salt and water into a uniform solution, heating to boil, cooling and crystallizing at a specific cooling rate, and calcining the obtained crystal to obtain a final product. The invention realizes the uniform doping of iron ions by utilizing the crystal self-crystallization, has simple preparation process and high yield, the obtained product is in a nanometer tube shape, the wall thickness is 3-20 nanometers, the thin-wall nanometer tube has large specific surface area and high reaction activity, and the iron ions are distributed in an oxazine ring network of C3N4, can not be oxidized and have important application in the field of energy materials.
Description
Technical Field
The invention relates to a preparation method of ion-doped carbon nitride, in particular to a preparation method of an iron ion-doped carbon nitride nanotube and an obtained product, and belongs to the technical field of semiconductor material preparation.
Background
Carbon nitride has attracted much attention in recent years as an organic semiconductor which is non-toxic, easily synthesized, stable in physicochemical properties, has a narrow bandgap (bandgap of about 2.7 ev), and has a high earth content. The carbon nitride of the graphite phase has a graphene-like layered structure and a series of properties similar to those of graphene, so that people search for the carbon nitride in a large quantity and apply the carbon nitride to the fields of photocatalytic degradation, photocatalytic hydrogen production, analytical chemistry and the like.
For carbon nitride, increasing carbon nitride active sites and ion doping are effective means for improving separation and transfer of photon-generated carriers. At present, many ion doping works are carried out, but the commonly adopted method is to grind nitrogen-containing organic precursors (such as melamine, dicyandiamide, thiourea and the like) and related salts at the early stage and synthesize the ion-doped carbon nitride through a thermal polycondensation process. However, the products obtained by the methods are blocky in appearance, most of the products have larger size and smaller specific surface area, and the product formed by calcination after grinding has uneven ion doping, because the ions are easy to diffuse to the surface in the thermal polycondensation process, and the ions on the surface of the carbon nitride are easy to oxidize. Therefore, it is of great research value to find a new ion doping method to solve the problems of non-uniform distribution of doped ions, easy oxidation of doped ions, large product size and small specific surface area.
In addition, the morphology of carbon nitride materials also has a significant impact on their performance. The shape of the carbon nitride nanotube is an effective way for improving a series of performances of photocatalytic hydrogen production, photocatalytic degradation of organic matters and the like, but no simple and convenient related reports of the ion-doped carbon nitride nanotube exist at present.
Disclosure of Invention
Aiming at the defects of nonuniform ion doping, easy oxidation of doped ions and the like in the existing preparation process of ion-doped carbon nitride, the invention provides a preparation method of an iron ion-doped carbon nitride nanotube and an obtained product.
The specific technical scheme of the invention is as follows:
a preparation method of iron ion doped carbon nitride nanotubes comprises the following steps:
(1) preparing a nitrogen-containing organic precursor, a ferric salt and water into a uniform solution;
(2) heating the uniform solution obtained in the step (1) to boiling, and then cooling to room temperature at a cooling rate of 1-5 ℃/min to crystallize;
(3) and calcining the precipitated crystal to obtain the iron ion doped carbon nitride nanotube.
The invention realizes the uniform doping of iron ions and the formation of the shape of the nanotube through two processes of crystallization and calcination. Firstly, preparing a solution consisting of a nitrogen-containing organic precursor, a ferric iron salt and water, wherein the nitrogen-containing organic precursor in the solution is in a supersaturated state, and heating the supersaturated solution to boiling and then feeding the supersaturated solution at a special cooling rateAnd cooling by stages, wherein the nitrogen-containing organic precursor crystal is gradually separated out in the cooling process, and iron ions are doped into the nitrogen-containing organic precursor crystal in the crystallization process. In the subsequent calcining process, the nitrogen-containing organic precursor crystal doped with iron ions is subjected to high-temperature thermal polycondensation to form the nanotube morphology. In the thermal polycondensation process, iron ions react with C3N4Nitrogen in (2) forms a coordinate bond and is fixed to C3N4Within the oxazine ring network, there is no diffusion to the surface. The existence of iron ions plays a role in promoting the generation of the carbon nitride nanotube appearance, and the stable existence of the iron ions is shown in C3N4The oxazine ring network is not oxidized and is uniformly distributed.
Further, in the step (1), when the homogeneous solution is prepared, the nitrogen-containing organic precursor is dissolved in water under heating and stirring in order to facilitate the dissolution of the nitrogen-containing organic precursor. For example, the nitrogen-containing organic precursor may be mixed with water, heated to reflux until the nitrogen-containing organic precursor is completely dissolved, and then added with ferric salt and mixed uniformly. The ferric salt is added as a solid or as an aqueous solution.
Furthermore, the composition and the temperature reduction process of the uniform solution in the step (1) have important influence on ion doping and the shape formation of the product. Preferably, the concentration of the nitrogen-containing organic precursor in the uniform solution of the nitrogen-containing organic precursor, the ferric salt and the water is 20-40 g/L. Preferably, the mass ratio of the nitrogen-containing organic precursor to the ferric salt is 100: 0.1-1.
Further, in the step (2), the heated uniform solution is cooled to room temperature according to the cooling rate of 1-5 ℃/min, and crystallization is carried out.
Further, the nitrogen-containing organic precursor is melamine or dicyandiamide, and the ferric salt is ferric chloride or ferric nitrate.
Further, in the step (3), the calcination temperature is 550-650 ℃, and the calcination time is 2-6 h. Preferably, the calcination is carried out at a temperature rise rate of 2-5 ℃/min up to 550-650 ℃.
Further, in the step (3), the calcination is performed under the protection of a gas, and the gas is preferably nitrogen or an inert gas.
The iron ion doped carbon nitride nanotube obtained by the method has the outer diameter of 200-800 nm and the wall thickness of 3-20 nm. The length of the nanotubes is typically 3-5 microns. The nanotube has thin wall and fluffy wall. The shape and the blocky shape prepared by the traditional method theoretically have higher specific surface area and better performance. The product obtained by the invention is also within the protection scope of the invention.
Furthermore, in the iron ion doped carbon nitride nanotube obtained by the invention, the XRD diffraction spectrum verifies that characteristic peaks related to iron elements do not appear in the XRD diffraction spectrum, so that the iron is shown to exist in the state of ferric ions in the nanotube. This side demonstrates that iron ions form coordinate bonds with N in carbon nitride during the preparation process and are fixed on C3N4In the oxazine ring network.
The method realizes the uniform doping of iron ions by utilizing the gradual self-crystallization of the crystal in the water phase environment, and prepares the iron ion doped carbon nitride nanotube.
The iron ion doped carbon nitride nanotube synthesized by the method has thin tube wall, and the nanotube is in a fluffy state, so that the exploration requirement of people on the aspect of improving the carbon nitride appearance is met. The shape of the invention is larger than the specific surface area of the traditional block shape, has higher reactivity, is beneficial to further improving the separation and transfer of the photo-generated electron hole pair, and has wide application prospect in the fields of photocatalytic degradation of organic matters, photocatalytic hydrogen production, energy materials, analytical chemistry and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a product obtained in example 1 of the present invention.
FIG. 2 is an X-ray diffraction (XRD) pattern of the product obtained in example 1 of the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of a product obtained in example 2 of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of a product obtained in comparative example 1 of the present invention.
FIG. 5 Scanning Electron Microscope (SEM) photograph of the product of the melamine calcination of comparative example 2 of the invention.
FIG. 6 Scanning Electron Microscope (SEM) photograph of the product obtained by calcining dicyandiamide of comparative example 2 of the present invention.
FIG. 7 is a Scanning Electron Microscope (SEM) photograph of a product obtained in comparative example 3 of the present invention.
FIG. 8 is a Scanning Electron Microscope (SEM) photograph of a product obtained in comparative example 4 of the present invention.
FIG. 9 is a Scanning Electron Microscope (SEM) photograph of a product obtained in comparative example 5 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should be understood as being merely illustrative and not limiting.
Example 1
1.1 2 g of melamine and 100 ml of deionized water are refluxed at 100 ℃ until the melamine is completely dissolved, giving an aqueous melamine solution.
1.2 preparing anhydrous ferric chloride into 0.02 g/ml ferric chloride aqueous solution, adding 100 microliter of the ferric chloride aqueous solution into the melamine aqueous solution, and refluxing for 30 min at 100 ℃ under stirring to fully and uniformly mix the melamine and the ferric chloride.
1.3, cooling the solution of the step 1.2 by stages, specifically: and (3) cooling the 1.2100 ℃ solution at the cooling rate of 1 ℃/min until the temperature is reduced to room temperature, and gradually separating out crystals in the cooling process.
1.4 after the crystallization is completed, taking out the precipitated crystal from the solution, and sucking the solution on the crystal on filter paper to obtain the iron-doped melamine crystal.
1.5 heating the obtained iron-doped melamine crystal to 550 ℃ at the heating rate of 2 ℃/min under the protection of argon gas, preserving heat for 4 h, and then naturally cooling along with the furnace.
1.6 grinding the calcined sample by using a mortar to obtain a final product.
FIG. 1 is a scanning electron micrograph of the product, from which it can be seen that the product is in the shape of a nanotube with a nanotube size of 3-5 microns, an outer diameter of 200-800 nm, a wall thickness of 3-20 nm, and the nanotube is in a fluffy state. The specific surface area is 87.9 m by the BET test2/g。
FIG. 2 is an X-ray diffraction pattern of the product, which shows only the characteristic peaks at 13.1 ℃ and 27.4 ℃ of graphite-phase carbon nitride, and does not show the characteristic peaks related to iron, thereby laterally demonstrating that iron exists in an ionic state and exists at C through coordination bonds3N4In the oxazine ring network.
Example 2
2.1 2 g of melamine and 100 ml of deionized water are refluxed at 100 ℃ until the melamine is completely dissolved, giving an aqueous melamine solution.
2.2 preparing anhydrous ferric chloride into 0.02 g/ml ferric chloride aqueous solution, adding 500 microliter of the ferric chloride aqueous solution into the melamine aqueous solution, and refluxing for 30 min at 100 ℃ under stirring to fully and uniformly mix the melamine and the ferric chloride.
2.3, cooling the solution of 2.2 by stages, specifically: and (3) cooling the 2.2100 ℃ solution at the cooling rate of 1 ℃/min until the temperature is reduced to room temperature, and gradually separating out crystals in the cooling process.
2.4 after the crystallization is completed, taking out the precipitated crystal from the solution, and sucking the solution on the crystal on filter paper to obtain the iron-doped melamine crystal.
2.5 heating the obtained iron-doped melamine crystal to 550 ℃ at the heating rate of 2 ℃/min under the protection of argon gas, preserving heat for 4 h, and then naturally cooling along with the furnace.
2.6 grinding the calcined sample by using a mortar to obtain the iron ion doped carbon nitride nanotube.
FIG. 3 is an SEM photograph of the obtained product, from which it can be seen that the obtained product is nanotubes of 3-5 μm, the nanotubes are in a fluffy state, the outer diameter is 200-800 nm, and the wall thickness is 10-20 nm. The ratio thereof by BET testSurface area of 86.2 m2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 3
3.1 refluxing 2 g of melamine with 100 ml of deionized water at 100 ℃ until the melamine is completely dissolved gives an aqueous melamine solution.
3.2 preparing anhydrous ferric chloride into 0.02 g/ml ferric chloride aqueous solution, adding 1 ml of ferric chloride aqueous solution into melamine aqueous solution, and refluxing for 30 min at 100 ℃ under stirring to fully and uniformly mix the melamine and the ferric chloride.
3.3, cooling the solution of 3.2 by stages, specifically: and (3) cooling the 3.2100 ℃ solution at the cooling rate of 1 ℃/min until the temperature is reduced to room temperature, and gradually separating out crystals in the cooling process.
3.4 after the crystallization is completed, taking out the precipitated crystal from the solution, and sucking the solution on the crystal on filter paper to obtain the iron-doped melamine crystal.
3.5 heating the obtained iron-doped melamine crystal to 550 ℃ at the heating rate of 2 ℃/min under the protection of argon gas, preserving heat for 4 h, and then naturally cooling along with the furnace.
3.6 grinding the calcined sample by using a mortar to obtain the iron ion doped carbon nitride nanotube. The carbon nitride nanotube is in a fluffy state, the size is 3-5 microns, the outer diameter is 200-800 nanometers, and the wall thickness is 13-20 nanometers. The specific surface area is 85.5 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 4
4.1 refluxing 4g dicyandiamide and 100 ml deionized water at 100 deg.C until dicyandiamide is completely dissolved to obtain dicyandiamide aqueous solution.
4.2 preparing anhydrous ferric chloride into ferric chloride aqueous solution with the concentration of 0.02 g/ml, adding 200 microliters of the ferric chloride aqueous solution into the dicyandiamide aqueous solution, and refluxing for 30 min at 100 ℃ under stirring to fully and uniformly mix the dicyandiamide and the ferric chloride.
4.3, cooling the solution of the 4.2 by stages, specifically: and (3) cooling the 4.2100 ℃ solution at the cooling rate of 1 ℃/min until the temperature is reduced to room temperature, and gradually separating out crystals in the cooling process.
4.4 after the crystallization is completed, taking out the precipitated crystal from the solution, and sucking the solution on the crystal on filter paper to obtain the iron-doped dicyandiamide crystal.
4.5 heating the obtained iron-doped dicyandiamide crystal to 550 ℃ at the heating rate of 2 ℃/min under the protection of argon gas, preserving heat for 4 h, and then naturally cooling along with the furnace.
And 4.6, grinding the calcined sample by using a mortar to obtain the iron ion doped carbon nitride nanotube. The morphology of the obtained product is basically similar to that of the product in the embodiment 1, the nanotube is in a fluffy state, the size is 3-5 microns, the outer diameter is 300-700 nanometers, and the wall thickness is 3-20 nanometers. The specific surface area is 85.3 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 5
Iron ion-doped carbon nitride nanotubes were prepared according to the method of example 1, except that: the ferric chloride was changed to ferric nitrate. The obtained iron ion doped carbon nitride nanotube has a similar appearance to that of the carbon nitride nanotube in example 1, is a fluffy nanotube, has a size of 3-5 microns, an outer diameter of 300-800 nm and a wall thickness of 5-20 nm. The specific surface area is 85.5 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 6
Iron ion-doped carbon nitride nanotubes were prepared as in example 2, except that: cooling according to the cooling rate of 3 ℃/min. The obtained iron ion doped carbon nitride nanotube is fluffy, the size is 3-5 microns, the outer diameter is 200-800 nanometers, and the wall thickness is 3-20 nanometers. The specific surface area is measured by BET86.1 m2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 7
Iron ion-doped carbon nitride nanotubes were prepared according to the method of example 3, except that: cooling according to the cooling rate of 2 ℃/min. The obtained iron ion doped carbon nitride nanotube is fluffy, the size is 3-5 microns, the outer diameter is 200-800 nanometers, and the wall thickness is 3-20 nanometers. The specific surface area is 87.1 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 8
Iron ion-doped carbon nitride nanotubes were prepared according to the method of example 1, except that: cooling according to the cooling rate of 5 ℃/min. The obtained iron ion doped carbon nitride nanotube is fluffy, the size is 3-4 microns, the outer diameter is 200-800 nanometers, and the wall thickness is 3-20 nanometers. The specific surface area is 86.4 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 9
Iron ion-doped carbon nitride nanotubes were prepared according to the method of example 1, except that: during calcination, the mixture is heated to 550 ℃ at the heating rate of 5 ℃/min, kept for 4 h and then naturally cooled along with the furnace. The obtained iron ion doped carbon nitride nanotube is fluffy, the size is 3-5 microns, the outer diameter is 200-800 nanometers, and the wall thickness is 10-20 nanometers. The specific surface area is 85.5 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 10
Iron ion-doped carbon nitride nanotubes were prepared according to the method of example 1, except that: the calcination temperature was 600 ℃. The obtained iron ion doped carbon nitride nanotube is fluffy and has a size of 3-5 μmThe outer diameter is 200-800 nm and the wall thickness is 5-15 nm. The specific surface area is 86.7 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 11
Iron ion-doped carbon nitride nanotubes were prepared according to the method of example 1, except that: the calcination temperature was 650 ℃. The obtained iron ion doped carbon nitride nanotube is fluffy, the size is 3-5 microns, the outer diameter is 200-800 nanometers, and the wall thickness is 3-10 nanometers. The specific surface area is 87.7 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 12
Iron ion-doped carbon nitride nanotubes were prepared according to the method of example 1, except that: the calcination time was 2 h. The obtained iron ion doped carbon nitride nanotube is fluffy, the size is 3-5 microns, the outer diameter is 200-800 nanometers, and the wall thickness is 15-20 nanometers. The specific surface area is 83.6 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Example 13
Iron ion-doped carbon nitride nanotubes were prepared according to the method of example 1, except that: the calcination time was 6 h. The obtained iron ion doped carbon nitride nanotube is fluffy, the size is 3-5 microns, the outer diameter is 200-800 nanometers, and the wall thickness is 3-12 nanometers. The specific surface area is 86.2 m by the BET test2(ii) in terms of/g. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and iron exists in C in ion state3N4In the oxazine ring network.
Comparative example 1
1.1 an aqueous melamine solution was prepared as in example 1.
1.2 preparing anhydrous ferric chloride into 0.02 g/ml ferric chloride aqueous solution, adding 100 microliter of the ferric chloride aqueous solution into the melamine aqueous solution, and refluxing for 30 min at 100 ℃ under stirring.
1.3, cooling the solution of 1.2 by stages, specifically: cooling to 10 deg.C, stirring for 10 min, and cooling to room temperature.
1.4 naturally airing the precipitated melamine crystals, heating to 550 ℃ at the heating rate of 2 ℃/min under the protection of argon gas, preserving heat for 4 hours, and then naturally cooling along with the furnace.
1.5 grinding the calcined sample by using a mortar to obtain a product.
FIG. 4 is a scanning electron micrograph of the resulting product. The photo shows that the obtained product has a flaky shape.
Comparative example 2
2.1 2 g of melamine or dicyandiamide and 100 ml of deionized water are refluxed at 100 ℃ until the melamine or dicyandiamide is completely dissolved.
2.2, cooling the solution of 2.1 by stages, specifically: and (3) cooling the 2.1100 ℃ solution at the cooling rate of 1 ℃/min until the temperature is reduced to room temperature, and gradually separating out crystals in the cooling process.
2.3 after complete crystallization, taking out the precipitated crystal from the solution, and sucking the solution on the crystal on filter paper;
2.4 heating the precipitated crystal to 550 ℃ at the heating rate of 2 ℃/min under the protection of argon gas, preserving heat for 4 h, and then naturally cooling along with the furnace.
2.5 grinding the calcined sample by using a mortar to obtain a final product.
FIG. 5 is a scanning electron micrograph of the product obtained by calcining melamine, and it can be seen from the micrograph that the product has a blocky morphology and no tubular morphology appears in the visual field. FIG. 6 is a scanning electron micrograph of the product obtained by calcining dicyandiamide, and it can be seen from the micrograph that the product also shows a blocky morphology, and no tubular morphology appears in the visual field.
Comparative example 3
Iron ion-doped carbon nitride was prepared according to the method of example 1, except that: melamine was changed to thiourea. The SEM image of the resulting product is shown in FIG. 7, and the product has a curled flake morphology with no tube morphology in the field.
Comparative example 4
4.1 refluxing 2 g of melamine with 100 ml of deionized water at 100 ℃ until the melamine is completely dissolved gives an aqueous melamine solution.
4.2 preparing anhydrous ferric chloride into 0.02 g/ml ferric chloride aqueous solution, adding 100 microliter of the ferric chloride aqueous solution into the melamine aqueous solution, and refluxing for 30 min at 100 ℃ under stirring.
4.3 naturally cooling the solution of 4.2 to room temperature.
4.4 naturally airing the precipitated melamine crystals, heating to 550 ℃ at the heating rate of 2 ℃/min under the protection of argon gas, preserving heat for 4 h, and then naturally cooling along with the furnace.
4.5 grinding the calcined sample with a mortar to obtain the final product.
FIG. 8 is a scanning electron micrograph of the resulting product. The obtained product is in a blocky shape with the stacked sheets, and no tubular shape appears in the visual field.
Comparative example 5
5.1 2 g of melamine and 0.02 g of ferric chloride were ground homogeneously in a mortar.
5.2 heating the obtained melamine mixed with the ferric iron to 550 ℃ at the heating rate of 2 ℃/min under the protection of argon gas, preserving the heat for 4 h, and then naturally cooling along with the furnace.
5.3 grinding the sample obtained in the step 5.2 by using a mortar to obtain a final product.
FIG. 9 is a scanning electron micrograph of the resulting product, which is foamy in morphology. Meanwhile, the product has magnetism, and part of ferric ions are oxidized into gamma-phase ferric oxide.
Comparative example 6
Iron ion-doped carbon nitride nanotubes were prepared according to the method of example 1, except that: heating to 550 ℃ at the heating rate of 10 ℃/min, preserving heat for 4 h, and then naturally cooling along with the furnace. The obtained product is in the form of tablet.
Claims (10)
1. A preparation method of iron ion doped carbon nitride nanotubes is characterized by comprising the following steps:
(1) preparing a nitrogen-containing organic precursor, a ferric salt and water into a uniform solution;
(2) heating the uniform solution obtained in the step (1) to boil, and then cooling to room temperature at a cooling rate of 1-5 ℃/min to crystallize;
(3) calcining the precipitated crystal to obtain an iron ion doped carbon nitride nanotube;
the nitrogen-containing organic precursor is melamine or dicyandiamide;
in the step (3), the temperature is raised to 550 ℃ and 650 ℃ at a temperature raising rate of 2-5 ℃/min for calcination.
2. The method of claim 1, wherein: the concentration of the nitrogen-containing organic precursor is 20-40g/L in the uniform solution of the nitrogen-containing organic precursor, the ferric salt and the water.
3. The method according to claim 1 or 2, characterized in that: the mass ratio of the nitrogen-containing organic precursor to the ferric iron salt is 100: 0.1-1.
4. The method according to claim 1 or 2, characterized in that: when the uniform solution is prepared in the step (1), firstly, mixing the nitrogen-containing organic precursor with water, heating to reflux until the nitrogen-containing organic precursor is completely dissolved, then adding the ferric salt, and uniformly mixing, wherein the ferric salt is added in a solid or aqueous solution form.
5. The method according to claim 1 or 2, characterized in that: the ferric salt is ferric chloride or ferric nitrate.
6. The method of claim 1, wherein: in the step (3), the calcination time is 2-6 h.
7. The method according to claim 1 or 6, wherein: in the step (3), the calcination is carried out under the protection of gas.
8. The method of claim 7, wherein: in the step (3), the gas is nitrogen or inert gas.
9. The method according to claim 1 or 2, characterized in that: the outer diameter of the iron ion doped carbon nitride nano tube is 200-800 nanometers, and the wall thickness is 3-20 nanometers; iron is uniformly distributed in C in a trivalent ion state3N4In the oxazine ring network.
10. Iron ion-doped carbon nitride nanotubes produced by the method for producing iron ion-doped carbon nitride nanotubes according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810140017.5A CN108339562B (en) | 2018-02-11 | 2018-02-11 | Preparation method of iron ion doped carbon nitride nanotube and obtained product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810140017.5A CN108339562B (en) | 2018-02-11 | 2018-02-11 | Preparation method of iron ion doped carbon nitride nanotube and obtained product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108339562A CN108339562A (en) | 2018-07-31 |
| CN108339562B true CN108339562B (en) | 2020-07-07 |
Family
ID=62959841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810140017.5A Expired - Fee Related CN108339562B (en) | 2018-02-11 | 2018-02-11 | Preparation method of iron ion doped carbon nitride nanotube and obtained product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108339562B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607498B (en) * | 2018-12-17 | 2020-06-02 | 山东大学 | g-C3N4Tetragonal nanotube photocatalyst and preparation method thereof |
| CN112007677A (en) * | 2020-07-24 | 2020-12-01 | 同济大学 | Nitrogen-doped iron nanotube, and preparation method and application thereof |
| CN113559908A (en) * | 2021-07-26 | 2021-10-29 | 深圳市康弘环保技术有限公司 | Ternary composite photocatalytic material, preparation method thereof and method for degrading PPCPs in water |
| CN113877621A (en) * | 2021-11-01 | 2022-01-04 | 武汉工程大学 | Red mud modified carbon nitride nano material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005089264A (en) * | 2003-09-18 | 2005-04-07 | Hidetoshi Saito | Carbon nitride substance containing metal and its manufacturing method, and hydrogen occlusion material |
| CN104986742A (en) * | 2015-06-29 | 2015-10-21 | 济南大学 | Bead-chain-like graphitized carbon nitride nano material and preparation method thereof |
| CN105271229A (en) * | 2015-10-10 | 2016-01-27 | 华南理工大学 | Method for in-situ preparation of iron carbide filled doped carbon nanotube |
| CN107324396A (en) * | 2017-06-06 | 2017-11-07 | 江苏大学 | A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite |
-
2018
- 2018-02-11 CN CN201810140017.5A patent/CN108339562B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005089264A (en) * | 2003-09-18 | 2005-04-07 | Hidetoshi Saito | Carbon nitride substance containing metal and its manufacturing method, and hydrogen occlusion material |
| CN104986742A (en) * | 2015-06-29 | 2015-10-21 | 济南大学 | Bead-chain-like graphitized carbon nitride nano material and preparation method thereof |
| CN105271229A (en) * | 2015-10-10 | 2016-01-27 | 华南理工大学 | Method for in-situ preparation of iron carbide filled doped carbon nanotube |
| CN107324396A (en) * | 2017-06-06 | 2017-11-07 | 江苏大学 | A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite |
Non-Patent Citations (2)
| Title |
|---|
| A review on g-C3N4-based photocatalysts;Jiuqing Wen et al.;《Applied Surface Science》;20160709;第391卷;第72-123页 * |
| Porous and low-defected graphitic carbon nitride nanotubes for efficient hydrogen evolution under visible light irradiation;Zhijun Huang et al.;《RSC Advances》;20151126;第5卷;第102700-102706页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108339562A (en) | 2018-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108339562B (en) | Preparation method of iron ion doped carbon nitride nanotube and obtained product | |
| Mu et al. | Synthesis, characterization, shape-preserved transformation, and optical properties of La (OH) 3, La2O2CO3, and La2O3 nanorods | |
| Li et al. | Preparation and characterization of Cu (OH) 2 and CuO nanowires by the coupling route of microemulsion with homogenous precipitation | |
| Salem et al. | Synthesis, structural and optical properties of Ni-doped ZnO micro-spheres | |
| Xu et al. | General and facile method to fabricate uniform Y 2 O 3: Ln 3+(Ln 3+= Eu 3+, Tb 3+) hollow microspheres using polystyrene spheres as templates | |
| Anas et al. | Studies on the evolution of ZnO morphologies in a thermohydrolysis technique and evaluation of their functional properties | |
| Liu et al. | Fabrication and photoluminescence properties of hollow Gd 2 O 3: Ln (Ln= Eu3+, Sm3+) spheres via a sacrificial template method | |
| Liu et al. | Shape-controlled synthesis of monodispersed nano-/micro-NaY (MoO 4) 2 (doped with Eu 3+) without capping agents via a hydrothermal process | |
| Zhang et al. | Synthesis of YAG powders by the co-precipitation method | |
| Su et al. | Preparation and characterization of Y3Al5O12 (YAG) nano-powder by co-precipitation method | |
| CN109650424B (en) | Amorphous alumina octahedral particle and preparation method thereof | |
| CN104671245B (en) | Preparation method of hafnium carbide nano-powder | |
| CN104973615B (en) | Microwave burning preparation method of nano gadolinium oxide powder | |
| CN108821311B (en) | Preparation method of prussian white mesomorphic material with fine and adjustable ferromanganese component | |
| Sun et al. | Synthesis of yttrium aluminum garnet (YAG) by a new sol–gel method | |
| Du et al. | Morphology and structure features of ZnAl2O4 spinel nanoparticles prepared by matrix-isolation-assisted calcination | |
| Zhong et al. | Gelatin-mediated hydrothermal synthesis of apple-like LaCO 3 OH hierarchical nanostructures and tunable white-light emission | |
| Zhang et al. | Uniform hollow TiO2: Sm3+ spheres: Solvothermal synthesis and luminescence properties | |
| Yang et al. | Hydrothermal synthesis, characterization and optical properties of La2Sn2O7: Eu3+ micro-octahedra | |
| KR20120115851A (en) | Manufacturing method of te and bismuth telluride nano wire by solvothermal synthesis | |
| CN108423648B (en) | Cobalt ion-doped carbon nitride hollow quadrangular prism and preparation method thereof | |
| Liu et al. | Electrochemical synthesis of In2O3 nanoparticles for fabricating ITO ceramics | |
| Kang et al. | Synthesis, morphology and optical properties of pure and Eu3+ doped β-Ga2O3 hollow nanostructures by hydrothermal method | |
| Liu et al. | Preparation and photoluminescence properties of Eu-doped Ga2O3 nanorods | |
| Zeng et al. | Uniform Eu3+: CeO2 hollow microspheres formation mechanism and optical performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200707 Termination date: 20210211 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |