CN108423648B - Cobalt ion-doped carbon nitride hollow quadrangular prism and preparation method thereof - Google Patents

Cobalt ion-doped carbon nitride hollow quadrangular prism and preparation method thereof Download PDF

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CN108423648B
CN108423648B CN201810195607.8A CN201810195607A CN108423648B CN 108423648 B CN108423648 B CN 108423648B CN 201810195607 A CN201810195607 A CN 201810195607A CN 108423648 B CN108423648 B CN 108423648B
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cobalt
quadrangular prism
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CN108423648A (en
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杨萍
江志翔
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University of Jinan
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Abstract

The invention discloses a cobalt ion doped carbon nitride hollow quadrangular prism and a preparation method thereof, wherein the side length of the outer side wall of the bottom surface of the hollow quadrangular prism is 300-400nm, the edge length is 4-10 mu m, and the wall thickness is 20-50 nm. The invention realizes the uniform doping of cobalt ions and the formation of hollow quadrangular prism appearance through two processes of crystallization and calcination. The invention utilizes the self-crystallization process of the crystal, not only can improve the purity of the raw material, but also realizes the uniform doping of cobalt ions, and has simple preparation process, good repeatability, high yield and universality. The product obtained by calcining has the shape of a hollow quadrangular prism, is novel and special, has a higher specific surface area than the traditional blocky shape, and has great application prospects in the fields of photocatalytic degradation of organic matters, photocatalytic hydrogen production, energy materials, analytical chemistry and the like. And cobalt ions are present in C3N4In the oxazine ring network, the cobalt ions are uniformly distributed and cannot be oxidized, so that the cobalt ions can be effectively prevented from being oxidized to form an oxide/carbon nitride heterojunction.

Description

Cobalt ion-doped carbon nitride hollow quadrangular prism and preparation method thereof
Technical Field
The invention relates to a cobalt ion doped carbon nitride hollow quadrangular prism with a special appearance and a preparation method thereof, belonging to the technical field of semiconductor material preparation.
Background
Carbon nitride is an organic semiconductor, has a band gap of about 2.7 ev, and is a photocatalytic material with great application potential. In recent years, a great deal of research is carried out on the carbon nitride material due to the excellent characteristics of low synthesis cost, no toxicity, stable physicochemical properties and the like, but the practical application of the carbon nitride material is greatly limited by the defects of poor conductivity, low specific surface area and the like of the carbon nitride.
Since 2009, a great deal of doping work has been carried out on carbon nitride by using a grinding method, and it has been found that the performance of the doped carbon nitride material is improved in the aspects of photocatalysis and the like. As a result, scientists have conducted extensive research in the field of carbon nitride doping, including metal ion doping and non-metal ion doping. However, the doped carbon nitride material synthesized by the grinding method is blocky in shape, most of the doped carbon nitride material has larger size and smaller specific surface area, and ions in a product formed by calcination after grinding are not uniformly doped, 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 the carbon nitride material also has important influence on the performance of the carbon nitride material, and can be used for improving a series of performances of photocatalytic hydrogen production, photocatalytic degradation of organic matters and the like. Therefore, the development of new forms of carbon nitride materials is also of great significance to the improvement of the properties of the carbon nitride materials.
Disclosure of Invention
Aiming at the defects of single appearance, nonuniform ion doping and the like of the existing ion-doped carbon nitride, the invention provides a cobalt ion-doped carbon nitride hollow quadrangular prism, which has special appearance, uniform cobalt ion doping and difficult oxidation.
The invention also provides a preparation method of the cobalt ion doped carbon nitride hollow quadrangular prism, the method is simple in operation process, good in repeatability and good in controllability, the obtained product is the hollow quadrangular prism, the appearance is special, the cobalt ions are uniformly distributed, and the cobalt ions are not easy to oxidize.
The invention realizes uniform doping of cobalt ions through self-crystallization, obtains the special shape of the hollow quadrangular prism at the same time, and overcomes the defects of uneven ion doping, single product shape, small specific surface area and the like of the traditional grinding method.
The specific technical scheme of the invention is as follows:
the cobalt ion doped carbon nitride hollow quadrangular prism has the length of 4-10 microns, the wall thickness of 20-50 nanometers, the bottom surface of the hollow quadrangular prism is quadrangular, and the side length of the outer side wall of the bottom surface is 300-400 nm. The shape and the blocky shape prepared by the traditional method theoretically have higher specific surface area and better performance.
Further, the carbon nitride is graphite phase carbon nitride.
Further, the hollow quadrangular prism is a hollow quadrangular prism.
Further, the cobalt is uniform in a state of divalent ionIs distributed at C3N4In the oxazine ring network, cobalt ions are not oxidized. The XRD diffraction spectrum verifies that characteristic peaks related to the cobalt element do not appear in the XRD diffraction spectrum, so that the cobalt is shown to exist in a state of divalent cobalt ions in the hollow quadrangular prism. This side demonstrates that cobalt ions form coordinate bonds with N in carbon nitride during preparation and are fixed to C3N4In the oxazine ring network.
The invention also provides a preparation method of the cobalt ion doped carbon nitride hollow quadrangular prism, which comprises the following steps:
(1) preparing a nitrogen-containing organic precursor, divalent cobalt salt and water into a uniform solution;
(2) heating the uniform solution obtained in the step (1) to boiling, then stopping heating, and cooling and crystallizing the boiled uniform solution in cold water;
(3) and calcining the precipitated crystal to obtain the cobalt ion doped carbon nitride hollow quadrangular prism.
The preparation process comprises two processes of crystallization and calcination, and the uniform doping of cobalt ions and the formation of the hollow quadrangular prism shape are realized through the two processes of crystallization and calcination. Firstly, preparing a solution consisting of a nitrogen-containing organic precursor, divalent cobalt salt and water, wherein the nitrogen-containing organic precursor in the solution is in a supersaturated state, heating the supersaturated solution to boiling, cooling and crystallizing, wherein the nitrogen-containing organic precursor crystal can be gradually separated out in the cooling process, and meanwhile, cobalt ions can be 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 cobalt ions is subjected to high-temperature thermal polycondensation to form a hollow quadrangular prism shape. In the thermal polycondensation process, cobalt 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 cobalt ions plays a role in promoting the generation of the shape of the carbon nitride hollow quadrangular prism, and the stable existence of the cobalt ions is shown in C3N4The oxazine ring network is not oxidized and is uniformly distributed.
Further, in the step (1), when the nitrogen-containing organic precursor is prepared as a homogeneous solution, the nitrogen-containing organic precursor may be dissolved in water under heating and stirring. For example, the nitrogen-containing organic precursor may be mixed with water, heated and refluxed until the nitrogen-containing organic precursor is completely dissolved, and then added with the divalent cobalt salt to be uniformly mixed. The divalent cobalt 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, in the homogeneous solution of the nitrogen-containing organic precursor, the divalent cobalt salt and water, the concentration of the nitrogen-containing organic precursor in the homogeneous solution is 0.06-0.1 g/mL. Preferably, the mass ratio of the divalent cobalt salt to the nitrogen-containing organic precursor is 1-2: 100.
further, in the step (1), the nitrogen-containing organic precursor is melamine or dicyandiamide. The nitrogen-containing organic precursor has certain influence on the formation of the product morphology, and the special morphology of the invention can not be formed by adopting other nitrogen-containing precursors such as thiourea, urea and the like.
Further, in the step (1), the divalent cobalt salt is cobalt chloride or cobalt nitrate.
Further, in the step (2), after the nitrogen-containing organic precursor and the divalent cobalt salt are fully and uniformly mixed in water, the uniform solution heated to boiling (100 ℃) is stopped heating, and the solution is directly put into ice water at the temperature of 0 ℃ for cooling and crystallization. The solution is rapidly cooled in ice water, and the formation of hollow quadrangular prism-shaped appearance is promoted.
Further, in the step (3), the calcination temperature is 550-. Preferably, the calcination is carried out at a temperature rise rate of 1-2 ℃/min up to 550-600 ℃.
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 invention utilizes the self-crystallization process of the crystal, not only can improve the purity of the raw material, but also realizes the uniform doping of cobalt ions, and has simple preparation process, good repeatability, high yield and universality. The product obtained by calcination has the hollow quadrangular appearance, and the appearance is novel,Special and single shape, higher specific surface area than the traditional block shape, and cobalt ion existing in C3N4In the oxazine ring network, the cobalt ions are uniformly distributed and cannot be oxidized, so that the cobalt ions can be effectively prevented from being oxidized to form an oxide/carbon nitride heterojunction.
The synthesized cobalt ion-doped carbon nitride hollow quadrangular prism has not been reported before, 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 a Scanning Electron Microscope (SEM) photograph of a product obtained in example 2 of the present invention.
FIG. 3 is an X-ray diffraction (XRD) pattern of the product obtained in example 1 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 is a Scanning Electron Microscope (SEM) photograph of a product obtained in comparative example 2 of the present invention.
FIG. 6 is a Scanning Electron Microscope (SEM) photograph of a product obtained in comparative example 3 of the present invention.
FIG. 7 is a Scanning Electron Microscope (SEM) photograph of a product obtained when the dopant ion of comparative example 4 of the present invention is manganese.
FIG. 8 is a Scanning Electron Microscope (SEM) photograph of a product obtained when comparative example 4 of the present invention is doped with nickel.
FIG. 9 is a Scanning Electron Microscope (SEM) photograph of a product obtained in comparative example 5 of the present invention.
FIG. 10 is a Scanning Electron Microscope (SEM) photograph of a product obtained in comparative example 6 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 an aqueous melamine solution was obtained by refluxing 8 g of melamine and 100 ml of deionized water at 100 c until the melamine was completely dissolved.
1.2 preparing cobalt chloride into 0.1g/ml aqueous solution of cobalt chloride, adding 800 microliter of aqueous solution of cobalt chloride into aqueous solution of melamine, and refluxing for 30 min at 100 ℃ under stirring to fully and uniformly mix the melamine and the cobalt chloride.
1.3 after the melamine and the cobalt chloride are fully and uniformly mixed, directly stopping heating, and directly putting the solution at the temperature of 100 ℃ into ice water at the temperature of 0 ℃ for rapid cooling to realize crystallization.
1.4 taking the precipitated crystal out of the solution, and sucking the solution on the crystal on filter paper to obtain the cobalt-doped melamine crystal.
1.5 heating the obtained cobalt-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 with a mortar to obtain the final product.
FIG. 1 is a scanning electron micrograph of the obtained product, from which it can be seen that the obtained product has a single morphology, is a hollow quadrangular prism, has edges perpendicular to the bottom surface, is a hollow quadrangular prism, has a bottom surface side length (side length of the outer side wall) of 300-400nm, a side length of 4-10 μm, and a wall thickness of 20-50 nm.
FIG. 3 is an X-ray diffraction pattern of the obtained 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 cobalt, thereby laterally demonstrating that cobalt exists in an ionic state and exists at C through a coordinate bond3N4In the oxazine ring network.
Example 2
2.1 refluxing 8 g of melamine with 100 ml of deionized water at 100 ℃ until the melamine is completely dissolved gives an aqueous melamine solution.
2.2 preparing the cobalt chloride into 0.1g/ml aqueous solution of the cobalt chloride, adding 1.6 ml of aqueous solution of the cobalt chloride into the aqueous solution of the melamine, and refluxing for 30 min at 100 ℃ under stirring to fully and uniformly mix the melamine and the cobalt chloride.
2.3 after the melamine and the cobalt chloride are fully and uniformly mixed, directly stopping heating, and directly putting the solution at the temperature of 100 ℃ into ice water at the temperature of 0 ℃ for rapid cooling to realize crystallization.
2.4 taking the precipitated crystal out of the solution, and sucking the solution on the crystal on filter paper to obtain the cobalt-doped melamine crystal.
2.5 heating the obtained cobalt-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 cobalt ion doped carbon nitride hollow quadrangular prism.
FIG. 2 is an SEM photograph of the product, which shows that the product is a hollow quadrangular prism with a bottom side length (the side length of the outer sidewall) of 320-400 nm, a wall thickness of 30-45 nm and a length of 5-8 μm. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Example 3
3.1 refluxing 8 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 the cobalt chloride into 0.1g/ml aqueous solution of the cobalt chloride, adding 1.2 ml of the aqueous solution of the cobalt chloride into the aqueous solution of the melamine, and refluxing for 30 min at 100 ℃ under stirring to fully and uniformly mix the melamine and the cobalt chloride.
3.3 after the melamine and the cobalt chloride are fully and uniformly mixed, directly stopping heating, and directly putting the solution at the temperature of 100 ℃ into ice water at the temperature of 0 ℃ for rapid cooling to realize crystallization.
3.4 taking the precipitated crystal out of the solution, and sucking the solution on the crystal on filter paper to obtain the cobalt-doped melamine crystal.
3.5 heating the obtained cobalt-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 cobalt ion doped carbon nitride hollow quadrangular prism. The side length of the bottom surface (the side length of the outer side wall) of the hollow quadrangular prism is 310-390 nanometers, the wall thickness is 35-50 nanometers, and the edge length is 5-10 micrometers. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Example 4
4.1 refluxing 8 g dicyandiamide and 100 ml deionized water at 100 deg.C until dicyandiamide is completely dissolved to obtain dicyandiamide aqueous solution.
4.2 preparing the cobalt chloride into a cobalt chloride aqueous solution with the concentration of 0.1g/ml, adding 800 microliters of the cobalt 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 cobalt chloride.
4.3 after the dicyandiamide and the cobalt chloride are fully and uniformly mixed, directly stopping heating, and directly putting the solution at the temperature of 100 ℃ into ice water at the temperature of 0 ℃ for rapid cooling to realize crystallization.
4.4 taking the precipitated crystal out of the solution, and sucking the solution on the crystal on filter paper to obtain the cobalt-doped dicyandiamide crystal.
4.5 heating the obtained cobalt-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.
4.6 grinding the calcined sample by using a mortar to obtain the cobalt ion-doped carbon nitride hollow quadrangular prism. The side length of the bottom surface (the side length of the outer side wall) of the hollow quadrangular prism is 320-400 nm, the wall thickness is 25-39 nm, and the edge length is 5-9 microns. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Example 5
Cobalt ion doped carbon nitride prepared according to the method of example 1A hollow quadrangular prism except that: cobalt chloride was exchanged for cobalt nitrate. The shape of the obtained hollow quadrangular prism is similar to that of the hollow quadrangular prism in the embodiment 1, the side length of the bottom surface (the side length of the outer side wall) is 360-400 nanometers, the wall thickness is 25-50 nanometers, and the edge length is 4-7 micrometers. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Example 6
A cobalt ion doped carbon nitride hollow tetraprism was prepared as in example 2 except that: cobalt chloride was exchanged for cobalt nitrate. The obtained hollow quadrangular prism has a shape similar to that of the hollow quadrangular prism in example 2, wherein the side length of the bottom surface (the side length of the outer side wall) is 310-385 nanometers, the wall thickness is 20-45 nanometers, and the edge length is 4-8 micrometers. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Example 7
A cobalt ion doped carbon nitride hollow tetraprism was prepared as in example 3 except that: cobalt chloride was exchanged for cobalt nitrate. The shape of the obtained hollow quadrangular prism is similar to that of the hollow quadrangular prism in the embodiment 3, the side length of the bottom surface (the side length of the outer side wall) is 350-400 nm, the wall thickness is 20-45 nm, and the edge length is 4-9 microns. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Example 8
A cobalt ion-doped carbon nitride hollow tetraprism was prepared as in example 1 except that: heating to 600 ℃ at the heating rate of 2 ℃/min, preserving heat for 4 h, and then naturally cooling along with the furnace. The shape of the obtained hollow quadrangular prism is similar to that of the hollow quadrangular prism in the embodiment 1, the side length of the bottom surface (the side length of the outer side wall) is 300-400 nanometers, the wall thickness is 20-50 nanometers, and the edge length is 4-10 micrometers. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Example 9
A cobalt ion-doped carbon nitride hollow tetraprism was prepared as in example 1 except that: at 1 deg.C/miAnd n, heating to 550 ℃ at the temperature rising speed, preserving heat for 4 h, and then naturally cooling along with the furnace. The shape of the obtained hollow quadrangular prism is similar to that of the hollow quadrangular prism in the embodiment 1, the side length of the bottom surface (the side length of the outer side wall) is 350-400 nanometers, the wall thickness is 24-45 nanometers, and the edge length is 5-9 micrometers. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Example 10
A cobalt ion-doped carbon nitride hollow tetraprism was prepared as in example 1 except that: heating to 550 ℃ at the heating rate of 1 ℃/min, preserving heat for 2 h, and then naturally cooling along with the furnace. The shape of the obtained hollow quadrangular prism is similar to that of the hollow quadrangular prism in example 1, the side length of the bottom surface (the side length of the outer side wall) is 320-390 nm, the wall thickness is 24-50 nm, and the edge length is 4-8 microns. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Example 11
A cobalt ion-doped carbon nitride hollow tetraprism was prepared as in example 1 except that: heating to 550 ℃ at the heating rate of 1 ℃/min, preserving heat for 6 h, and then naturally cooling along with the furnace. The shape of the obtained hollow quadrangular prism is similar to that of the hollow quadrangular prism in the embodiment 1, the side length of the bottom surface (the side length of the outer side wall) is 330-400 nanometers, the wall thickness is 20-40 nanometers, and the edge length is 5-9 micrometers. The product is graphite phase carbon nitride verified by X-ray diffraction pattern, and cobalt exists in C in ion state3N4In the oxazine ring network.
Comparative example 1
1.1 an aqueous melamine solution was obtained by refluxing 8 g of melamine and 100 ml of deionized water at 100 c until the melamine was completely dissolved.
1.2 after the melamine is completely dissolved, directly stopping heating, and directly putting the solution at 100 ℃ into ice water at 0 ℃ for rapid cooling to realize crystallization.
1.3 naturally airing the precipitated crystal, 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.
1.5 grinding the calcined sample by using a mortar to obtain a final product.
FIG. 4 is a scanning electron micrograph of the resulting product, from which it can be seen that the resulting product has a multilayer lamellar morphology.
Comparative example 2
2.1 refluxing 8 g of melamine with 100 ml of deionized water at 100 ℃ until the melamine is completely dissolved gives an aqueous melamine solution.
2.2 preparing the cobalt chloride into 0.1g/ml aqueous solution of the cobalt chloride, adding 800 microliter of the aqueous solution of the cobalt chloride into the aqueous solution of the melamine, and refluxing for 30 min at 100 ℃ under stirring to fully and uniformly mix the melamine and the cobalt chloride.
And 2.3 directly stopping heating after the melamine and the cobalt chloride are fully and uniformly mixed, and directly pouring the solution into liquid nitrogen for rapid cooling.
2.4 naturally airing the precipitated crystal, 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.
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, from which it can be seen that the product obtained is mainly in the form of blocks.
Comparative example 3
A cobalt ion-doped carbon nitride hollow tetraprism was prepared as in example 1 except that: heating to 650 ℃ at the heating rate of 2 ℃/min, preserving heat for 4 h, and then naturally cooling along with the furnace.
The SEM image of the obtained product is shown in FIG. 6, and it can be seen that the obtained product has a thin-walled tubular shape and a quadrangular prism shape disappears.
Comparative example 4
A cobalt ion-doped carbon nitride hollow tetraprism was prepared as in example 1 except that: the cobalt chloride is replaced by manganese chloride and nickel chloride respectively.
FIGS. 7 to 8 are SEM images of the products obtained from manganese chloride and nickel chloride, respectively, and it can be seen that the obtained products have tubular shapes with different shapes and the quadrangular prism shape disappears.
Comparative example 5
5.1 an aqueous melamine solution was obtained by refluxing 8 g of melamine and 100 ml of deionized water at 100 c until the melamine was completely dissolved.
5.2 preparing ferric chloride into 0.1g/ml ferric chloride aqueous solution, adding 800 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.
5.3 after the melamine and the ferric chloride are fully and uniformly mixed, directly stopping heating, and cooling the solution at the temperature of 100 ℃ at the cooling rate of 1 ℃/min until the temperature is reduced to the room temperature, thereby realizing crystallization.
And 5.4, taking the precipitated crystals out of the solution, and sucking the solution on the crystals on filter paper to obtain the iron-doped melamine crystals.
5.5 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.
5.6 grinding the calcined sample by using a mortar to obtain the final product.
Fig. 9 is an SEM image of the resulting product, from which it can be seen that the resulting product has a fluffy tubular morphology and a quadrangular prism morphology disappears.
Comparative example 6
6.1 an aqueous melamine solution was obtained by refluxing 8 g of melamine and 100 ml of deionized water at 100 ℃ until the melamine was completely dissolved.
6.2 preparing the cobalt chloride into 0.1g/ml aqueous solution of the cobalt chloride, adding 800 microliter of the aqueous solution of the cobalt chloride into the aqueous solution of the melamine, and refluxing for 30 min at 100 ℃ under stirring to fully and uniformly mix the melamine and the cobalt chloride.
6.3 after the melamine and the cobalt chloride are fully and uniformly mixed, the temperature of the solution is maintained at 80 ℃ so that the crystal grows slowly.
6.4 taking the grown crystal out of the solution, and sucking the solution on the crystal on filter paper to obtain the cobalt-doped melamine crystal.
6.5 heating the obtained cobalt-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.
6.6 grinding the calcined sample with a mortar to obtain the final product.
The SEM image of the resulting product is shown in FIG. 10, from which it can be seen that the resulting product is a bulk morphology.

Claims (11)

1. A cobalt ion doped carbon nitride hollow quadrangular prism is characterized in that: the side length of the outer side wall of the bottom surface of the hollow quadrangular prism is 300-400nm, the edge length is 4-10 mu m, and the wall thickness is 20-50 nm.
2. The cobalt ion doped carbon nitride hollow quadrangular prism as claimed in claim 1, wherein: the hollow quadrangular prism is a hollow quadrangular prism.
3. The cobalt ion doped carbon nitride hollow quadrangular prism as claimed in claim 1 or 2, wherein: the cobalt is uniformly distributed in C in a divalent ion state3N4In the oxazine ring network.
4. A method of making a cobalt ion doped carbon nitride hollow quadrangular prism as claimed in any one of claims 1 to 3, comprising the steps of:
(1) preparing a nitrogen-containing organic precursor, divalent cobalt salt and water into a uniform solution;
(2) heating the uniform solution obtained in the step (1) to boiling, then stopping heating, and cooling and crystallizing the boiled uniform solution in cold water;
(3) calcining the precipitated crystal to obtain a cobalt ion doped carbon nitride hollow quadrangular prism;
in the step (3), the calcination is carried out under the protection of gas, and the calcination temperature is 550-600 ℃.
5. The method according to claim 4, wherein: in the step (1), when preparing the uniform solution, firstly mixing the nitrogen-containing organic precursor with water, heating and refluxing until the nitrogen-containing organic precursor is completely dissolved, then adding divalent cobalt salt, and uniformly mixing, wherein the divalent cobalt salt is added in a solid or aqueous solution form.
6. The method according to claim 4, wherein: in the step (2), the boiling uniform solution is directly put into ice water with the temperature of 0 ℃ for cooling and crystallization.
7. The method of claim 4, 5 or 6, wherein: in the step (1), the concentration of the nitrogen-containing organic precursor in the uniform solution is 0.06-0.1 g/mL; the mass ratio of the divalent cobalt salt to the nitrogen-containing organic precursor is 1-2: 100.
8. the method of claim 4, 5 or 6, wherein: in the step (1), the nitrogen-containing organic precursor is melamine or dicyandiamide, and the divalent cobalt salt is cobalt chloride or cobalt nitrate.
9. The method according to claim 4, wherein: in the step (3), the calcination time is 2-6 h.
10. The method according to claim 4 or 9, wherein: in the step (3), the temperature is raised to 550 ℃ and 600 ℃ at the temperature rise speed of 1-2 ℃/min for calcination; the gas is an inert gas.
11. The method according to claim 4 or 9, wherein: in the step (3), the gas is nitrogen.
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