CN108423648A - A kind of hollow quadrangular of the carbonitride of ZnO thin film and preparation method thereof - Google Patents
A kind of hollow quadrangular of the carbonitride of ZnO thin film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of hollow quadrangular of the carbonitride of ZnO thin film and preparation method thereof, the outer side bottom surface wall length of side of hollow quadrangular is 300 400nm, and a length of 4 10 μm of rib, wall thickness is 20 50 nanometers.The present invention realizes the formation of the Uniform Doped and hollow quadrangular pattern of cobalt ions by two processes of crystallization and calcining.The present invention, from Crystallization Process, not only can be improved the purity of raw material, also achieve the Uniform Doped of cobalt ions using crystal, and preparation process is simple, reproducible, and yield is high, and have universality.Calcining obtained product has a hollow quadrangular pattern, the novel in shape, special, has higher specific surface area than traditional bulk morphologies, in the great application prospect in the fields such as photocatalytic degradation organic matter, Photocatalyzed Hydrogen Production, energy and material, analytical chemistry.And cobalt ions is present in C3N4It in piperazine loop network, is evenly distributed and will not be oxidized, cobalt ions generation oxidation can be effectively prevented from and form oxide/carbonitride hetero-junctions.
Description
Technical field
The present invention relates to hollow quadrangulars of carbonitride of a kind of ZnO thin film that pattern is special and preparation method thereof, belong to
Technical field of semiconductor material preparation.
Background technology
For carbonitride as a kind of organic semiconductor, band gap is about 2.7 ev, is a kind of photocatalysis of great application potential
Material.Since it is relatively low with synthesis cost, nontoxic and the excellent specific properties such as physicochemical properties stabilization, people were to it in recent years
A large amount of exploration is carried out, but the disadvantages such as carbonitride poorly conductive, specific surface area be low significantly limit carbon nitride material
Practical application.
Since two thousand nine, people have carried out a large amount of doping work using polishing to carbonitride, and after finding doping
Carbon nitride material get a promotion in photocatalysis etc. performance.Therefore, scientific worker to carbonitride adulterate this field into
A large amount of exploration is gone, including metal ion mixing and nonmetallic ion-doped.But the doping carbonitride synthesized with polishing
Material morphology is bulk, and most size is larger, and specific surface area is smaller, and the product intermediate ion doping that formation is calcined after grinding is uneven
Even, because easily being diffused to the surface in thermal polycondensation process intermediate ion, the ion for nitrogenizing carbon surface is easy oxidation.Therefore, one is found
The new ion doping method of kind is unevenly distributed with solving Doped ions, Doped ions are oxidizable, product size is big, specific surface area
Small problem is great researching value.
In addition, the pattern of carbon nitride material to its performance also important, can be used for improving its Photocatalyzed Hydrogen Production, light
The a series of performance such as catalytic degradation organic matter.Therefore the new pattern of exploitation carbon nitride material also has the raising of its performance important
Meaning.
Invention content
For the deficiencies of existing ion doping type carbonitride pattern is single, ion doping is uneven, the present invention provides one
The hollow quadrangular of carbonitride of kind ZnO thin film, the product pattern is special, and ZnO thin film is uniform, not oxidizable.
The present invention also provides the preparation method of the hollow quadrangular of the carbonitride of above-mentioned ZnO thin film, this method operated
Journey is simple, reproducible, and controllability is good, and products obtained therefrom is hollow quadrangular, and pattern is special, and cobalt ions is evenly distributed, is not easy
Oxidation.
The present invention has obtained hollow quadrangular special appearance by realizing the Uniform Doped of cobalt ions from crystallization, gram
The defects of traditional polishing ion doping is uneven, product pattern is single, product specific surface area is small is taken.
Specific technical solution of the present invention is as follows：
A kind of hollow quadrangular of the carbonitride of ZnO thin film, a length of 4-10 μm of the rib of the hollow quadrangular, wall thickness is received for 20-50
The bottom surface of rice, hollow quadrangular is quadrangle, and the length of side of the lateral wall of bottom surface is 300-400nm.The pattern and conventional method system
The bulk morphologies obtained theoretically have higher specific surface area, and performance is more preferably.
Further, the carbonitride is graphite phase carbon nitride.
Further, the hollow quadrangular is four hollow right prisms.
Further, the cobalt is evenly distributed on C with bivalent ions state3N4In piperazine loop network, therefore cobalt ions will not
It is aoxidized.Verified through XRD diffraction spectras, occur in XRD diffraction spectras with the relevant characteristic peak of cobalt element, therefore show cobalt in sky
Exist really with the state of divalent cobalt ion in heart quadrangular.This side demonstrates cobalt ions and carbonitride during preparation
In N form coordinate bond, be fixed on C3N4In piperazine loop network.
The present invention also provides the preparation method of the hollow quadrangular of the carbonitride of ZnO thin film, this method includes following step
Suddenly：
（1）Nitrogenous organic precursor, divalent cobalt and water are made into homogeneous solution；
（2）By step（1）Homogeneous solution be heated to boiling, then stop heating, the homogeneous solution of boiling is dropped in cold water
Warm crystallization；
（3）The crystal of precipitation is calcined, the hollow quadrangular of carbonitride of ZnO thin film is obtained.
Preparation process of the present invention includes two processes of crystallization and calcining, and cobalt ions is realized by two processes of crystallization and calcining
Uniform Doped and hollow quadrangular pattern formation.First, the molten of nitrogenous organic precursor, divalent cobalt and water composition is prepared
Liquid, nitrogenous organic precursor is in hypersaturated state in the solution, which is cooled down crystallization after being heated to boiling, is contained
Nitrogen organic precursor crystal can gradually be precipitated during cooling, while cobalt ions can be adulterated into containing during crystallization
In nitrogen organic precursor crystal.In subsequent calcination process, doped with cobalt ions nitrogenous organic precursor crystal through excessively high
Polycondensation is warmed, hollow quadrangular pattern is formed.During thermal polycondensation, cobalt ions and C3N4In nitrogen formed coordinate bond, quilt
It is fixed on C3N4In piperazine loop network, do not diffuse to the surface.The presence of cobalt ions plays the generation of the hollow quadrangular pattern of carbonitride
Facilitation is arrived, the presence that cobalt ions is stablized is in C3N4It in piperazine loop network, will not be oxidized, and be evenly distributed.
Further, above-mentioned steps（1）In, when preparing homogeneous solution, the dissolving of nitrogenous organic precursor for convenience can
To be dissolved in water in the case of heating, stirring.For example, can first mix nitrogenous organic precursor with water, heat
It is back to nitrogenous organic precursor to be completely dissolved, divalent cobalt is then added and is uniformly mixed.The divalent cobalt is with solid or water
The form of solution is 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, divalent cobalt and water, nitrogenous organic precursor is equal
A concentration of 0.06-0.1g/mL in even solution.Preferably, the mass ratio of divalent cobalt and nitrogenous organic precursor is 1 ~ 2：
100。
Further, step（1）In, the nitrogenous organic precursor is melamine or dicyandiamide.Nitrogenous organosilane precursor
Body has certain influence to the formation of product pattern, and the present invention cannot be formed such as thiocarbamide, urea using other nitrogenous precursors
Special appearance.
Further, step（1）In, the divalent cobalt is cobalt chloride or cobalt nitrate.
Further, step（2）In, it, will after nitrogenous organic precursor and divalent cobalt are sufficiently mixed uniformly in water
It is heated to boiling（100℃）Homogeneous solution stop heating, be directly placed into 0 DEG C of ice water the crystallization that cools down.Solution is in ice water
It is quickly cooled down, promotes the formation of hollow quadrangular shape pattern.
Further, step（3）In, calcination temperature is 550-600 DEG C, and calcination time is 2-6 h.Preferably, with 1-2
DEG C/heating rate of min rises to 550-600 DEG C and calcined.
Further, step（3）In, calcining carries out under gas shield, and the gas is preferably nitrogen or inert gas.
The present invention, from Crystallization Process, not only can be improved the purity of raw material, also achieve the uniform of cobalt ions using crystal
Doping, preparation process is simple, reproducible, and yield is high, and has universality.Calcining obtained product has hollow four prism type
Looks, it is the novel in shape, special, single, there is higher specific surface area than traditional bulk morphologies, and cobalt ions exists in C3N4
It in piperazine loop network, is evenly distributed and will not be oxidized, cobalt ions generation oxidation can be effectively prevented from and form oxide/carbonitride
Hetero-junctions.
It is had not been reported before the hollow quadrangular of carbonitride for the ZnO thin film that the present invention synthesizes, this satisfies people to nitrogen
Change the exploration demand in terms of carbon pattern improvement.Pattern of the present invention has higher anti-than traditional bulk morphologies large specific surface area
Activity is answered, the separation for further increasing photo-generate electron-hole pair and transfer are conducive to, is produced in photocatalytic degradation organic matter, photocatalysis
The great application prospect in the fields such as hydrogen, 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.
The scanning electron microscope of 2 products obtained therefrom of Fig. 2 embodiment of the present invention（SEM）Photo.
The X-ray diffraction of 1 products obtained therefrom of Fig. 3 embodiment of the present invention（XRD）Collection of illustrative plates.
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 products obtained therefroms of comparative example of the present invention（SEM）Photo.
The scanning electron microscope of Fig. 63 products obtained therefroms of comparative example of the present invention（SEM）Photo.
The scanning electron microscope of products obtained therefrom when Fig. 74 Doped ions of comparative example of the present invention are manganese（SEM）Photo.
The scanning electron microscope of products obtained therefrom when Fig. 84 Doped ions of comparative example of the present invention are nickel（SEM）Photo.
The scanning electron microscope of Fig. 95 products obtained therefroms of comparative example of the present invention（SEM）Photo.
The scanning electron microscope of Figure 10 6 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 8 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 cobalt chloride the cobalt chloride solution of a concentration of 0.1 g/ml, and 800 microlitres of cobalt chloride solutions are added
Enter in melamine aqueous solution, under stiring, 100 DEG C reflux 30 min, so that melamine and cobalt chloride is sufficiently mixed uniformly.
1.3 after melamine and cobalt chloride are sufficiently mixed uniformly, directly stop heating, and 100 DEG C of solution is direct
It is put into 0 DEG C of ice water and is quickly cooled down, realize crystallization.
1.4 take out the crystal of precipitation from solution, and the solution on crystal is blotted on filter paper, obtain the trimerization of cobalt doped
Cyanamide crystal.
1.5 by the melamine crystals of cobalt doped 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.
The 1.6 sample mortar grinders for obtaining 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 pattern is single, it is hollow four
Prism-shaped, the rib and plane perpendicular of hollow quadrangular are hollow four right prism, the bottom surface length of side of hollow quadrangular（Lateral wall
The length of side）It it is 300-400 nanometers, a length of 4-10 μm of rib, wall thickness is 20-50 nanometers.
Fig. 3 is the X ray diffracting spectrum of products obtained therefrom, and 13.1 ° and 27.4 ° of graphite phase carbon nitride are only shown in collection of illustrative plates
Characteristic peak, do not occur with the relevant characteristic peak of cobalt, it is possible thereby to side prove cobalt exist with ionic condition, pass through coordination
Key exists in C3N4In piperazine loop network.
Embodiment 2
2.1 flow back 8 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 cobalt chloride the cobalt chloride solution of a concentration of 0.1 g/ml, and 1.6 milliliters of cobalt chloride solutions are added
Enter in melamine aqueous solution, under stiring, 100 DEG C reflux 30 min, so that melamine and cobalt chloride is sufficiently mixed uniformly.
2.3 after melamine and cobalt chloride are sufficiently mixed uniformly, directly stop heating, and 100 DEG C of solution is direct
It is put into 0 DEG C of ice water and is quickly cooled down, realize crystallization.
2.4 take out the crystal of precipitation from solution, and the solution on crystal is blotted on filter paper, obtain the trimerization of cobalt doped
Cyanamide crystal.
2.5 by the melamine crystals of cobalt doped 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.
The 2.6 sample mortar grinders for obtaining calcining, obtain the hollow quadrangular of carbonitride of ZnO thin film.
Fig. 2 is the SEM photograph of products obtained therefrom, it can be seen from the figure that products obtained therefrom is hollow quadrangular, the bottom surface length of side
（The length of side of lateral wall）It it is 320-400 nanometers, wall thickness is 30-45 nanometers, and rib is 5-8 microns a length of.It is tested through X ray diffracting spectrum
Card, product are graphite phase carbon nitride, and cobalt exists with ionic condition in C3N4In piperazine loop network.
Embodiment 3
3.1 flow back 8 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 cobalt chloride the cobalt chloride solution of a concentration of 0.1 g/ml, and 1.2 milliliters of cobalt chloride solutions are added
Enter in melamine aqueous solution, under stiring, 100 DEG C reflux 30 min, so that melamine and cobalt chloride is sufficiently mixed uniformly.
3.3 after melamine and cobalt chloride are sufficiently mixed uniformly, directly stop heating, and 100 DEG C of solution is direct
It is put into 0 DEG C of ice water and is quickly cooled down, realize crystallization.
3.4 take out the crystal of precipitation from solution, and the solution on crystal is blotted on filter paper, obtain the trimerization of cobalt doped
Cyanamide crystal.
3.5 by the melamine crystals of cobalt doped 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.
The 3.6 sample mortar grinders for obtaining calcining, obtain the hollow quadrangular of carbonitride of ZnO thin film.It is hollow
The quadrangular bottom surface length of side（The length of side of lateral wall）It it is 310-390 nanometers, wall thickness is 35-50 nanometers, a length of 5-10 μm of rib.It is penetrated through X
Ray diffraction diagram spectrum verification, product are graphite phase carbon nitride, and cobalt exists with ionic condition in C3N4In piperazine loop network.
Embodiment 4
4.1 flow back 8 g dicyandiamides and 100 ml deionized waters at 100 DEG C, until dicyandiamide is completely dissolved, obtain double cyanogen
Amine aqueous solution.
4.2 are made into cobalt chloride the cobalt chloride solution of a concentration of 0.1 g/ml, and 800 microlitres of cobalt chloride solutions are added
Enter in dicyandiamide aqueous solution, under stiring, 100 DEG C reflux 30 min, so that dicyandiamide and cobalt chloride is sufficiently mixed uniformly.
4.3 after dicyandiamide and cobalt chloride are sufficiently mixed uniformly, directly stop heating, and 100 DEG C of solution is directly put
Enter and be quickly cooled down in 0 DEG C of ice water, realizes crystallization.
4.4 take out the crystal of precipitation from solution, and the solution on crystal is blotted on filter paper, obtain double cyanogen of cobalt doped
Amine crystal.
4.5 by the dicyandiamide crystal of cobalt doped 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.
The 4.6 sample mortar grinders for obtaining calcining, obtain the hollow quadrangular of carbonitride of ZnO thin film.It is hollow
The quadrangular bottom surface length of side（The length of side of lateral wall）It it is 320-400 nanometers, wall thickness is 25-39 nanometers, and rib is 5-9 microns a length of.It is penetrated through X
Ray diffraction diagram spectrum verification, product are graphite phase carbon nitride, and cobalt exists with ionic condition in C3N4In piperazine loop network.
Embodiment 5
The hollow quadrangular of carbonitride of ZnO thin film is prepared according to the method for embodiment 1, unlike：Cobalt chloride is changed to nitre
Sour cobalt.The hollow quadrangular pattern of gained is similar to Example 1, the bottom surface length of side（The length of side of lateral wall）It is 360-400 nanometers, wall
Thickness is 25-50 nanometers, and rib is 4-7 microns a length of.It is verified through X ray diffracting spectrum, product is graphite phase carbon nitride, and cobalt is with ion like
State exists in C3N4In piperazine loop network.
Embodiment 6
The hollow quadrangular of carbonitride of ZnO thin film is prepared according to the method for embodiment 2, unlike：Cobalt chloride is changed to nitre
Sour cobalt.The hollow quadrangular pattern of gained is similar to Example 2, the bottom surface length of side（The length of side of lateral wall）It is 310-385 nanometers, wall
Thickness is 20-45 nanometers, and rib is 4-8 microns a length of.It is verified through X ray diffracting spectrum, product is graphite phase carbon nitride, and cobalt is with ion like
State exists in C3N4In piperazine loop network.
Embodiment 7
The hollow quadrangular of carbonitride of ZnO thin film is prepared according to the method for embodiment 3, unlike：Cobalt chloride is changed to nitre
Sour cobalt.The hollow quadrangular pattern of gained is similar to Example 3, the bottom surface length of side（The length of side of lateral wall）It is 350-400 nanometers, wall
Thickness is 20-45 nanometers, and rib is 4-9 microns a length of.It is verified through X ray diffracting spectrum, product is graphite phase carbon nitride, and cobalt is with ion like
State exists in C3N4In piperazine loop network.
Embodiment 8
The hollow quadrangular of carbonitride of ZnO thin film is prepared according to the method for embodiment 1, unlike：With 2 DEG C/min's
Heating rate is heated to 600 DEG C, and keeps the temperature 4 h, later with stove natural cooling.The hollow quadrangular pattern of gained and 1 class of embodiment
Seemingly, the bottom surface length of side（The length of side of lateral wall）It it is 300-400 nanometers, wall thickness is 20-50 nanometers, and rib is 4-10 microns a length of.It is penetrated through X
Ray diffraction diagram spectrum verification, product are graphite phase carbon nitride, and cobalt exists with ionic condition in C3N4In piperazine loop network.
Embodiment 9
The hollow quadrangular of carbonitride of ZnO thin film is prepared according to the method for embodiment 1, unlike：With 1 DEG C/min's
Heating rate is heated to 550 DEG C, and keeps the temperature 4 h, later with stove natural cooling.The hollow quadrangular pattern of gained and 1 class of embodiment
Seemingly, the bottom surface length of side（The length of side of lateral wall）It it is 350-400 nanometers, wall thickness is 24-45 nanometers, and rib is 5-9 microns a length of.It is penetrated through X
Ray diffraction diagram spectrum verification, product are graphite phase carbon nitride, and cobalt exists with ionic condition in C3N4In piperazine loop network.
Embodiment 10
The hollow quadrangular of carbonitride of ZnO thin film is prepared according to the method for embodiment 1, unlike：With 1 DEG C/min's
Heating rate is heated to 550 DEG C, and keeps the temperature 2 h, later with stove natural cooling.The hollow quadrangular pattern of gained and 1 class of embodiment
Seemingly, the bottom surface length of side（The length of side of lateral wall）It it is 320-390 nanometers, wall thickness is 24-50 nanometers, and rib is 4-8 microns a length of.It is penetrated through X
Ray diffraction diagram spectrum verification, product are graphite phase carbon nitride, and cobalt exists with ionic condition in C3N4In piperazine loop network.
Embodiment 11
The hollow quadrangular of carbonitride of ZnO thin film is prepared according to the method for embodiment 1, unlike：With 1 DEG C/min's
Heating rate is heated to 550 DEG C, and keeps the temperature 6 h, later with stove natural cooling.The hollow quadrangular pattern of gained and 1 class of embodiment
Seemingly, the bottom surface length of side（The length of side of lateral wall）It it is 330-400 nanometers, wall thickness is 20-40 nanometers, and rib is 5-9 microns a length of.It is penetrated through X
Ray diffraction diagram spectrum verification, product are graphite phase carbon nitride, and cobalt exists with ionic condition in C3N4In piperazine loop network.
Comparative example 1
1.1 flow back 8 g melamines and 100 ml deionized waters at 100 DEG C, until melamine is completely dissolved, obtain
Melamine aqueous solution.
1.2 after melamine is completely dissolved, and directly stops heating, and 100 DEG C of solution is directly placed into 0 DEG C of ice water
In be quickly cooled down, realize crystallization.
1.3 dry the natural crystal of precipitation, are heated to the heating rate of 2 DEG C/min under argon gas protection
550 DEG C, and 4 h are kept the temperature, later with stove natural cooling.
The 1.5 sample mortar grinders for obtaining calcining, obtain final products.
Fig. 4 is the stereoscan photograph of products obtained therefrom, it can be seen from the figure that products obtained therefrom is multilayer chip pattern.
Comparative example 2
2.1 flow back 8 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 cobalt chloride the cobalt chloride solution of a concentration of 0.1 g/ml, and 800 microlitres of cobalt chloride solutions are added
Enter in melamine aqueous solution, under stiring, 100 DEG C reflux 30 min, so that melamine and cobalt chloride is sufficiently mixed uniformly.
2.3 after melamine and cobalt chloride are sufficiently mixed uniformly, directly stop heating, solution is directly poured into liquid nitrogen,
Carry out fast cooling.
2.4 dry the natural crystal of precipitation, are heated to the heating rate of 2 DEG C/min under argon gas protection
550 DEG C, and 4 h are kept the temperature, later with stove natural cooling.
The 2.5 sample mortar grinders for obtaining calcining, obtain final products.
Fig. 5 is the stereoscan photograph of products obtained therefrom, it can be seen from the figure that products obtained therefrom is mainly bulk morphologies.
Comparative example 3
The hollow quadrangular of carbonitride of ZnO thin film is prepared according to the method for embodiment 1, unlike：With 2 DEG C/min's
Heating rate is heated to 650 DEG C, and keeps the temperature 4 h, later with stove natural cooling.
The SEM of products obtained therefrom schemes as shown in fig. 6, it can be seen from the figure that products obtained therefrom is thin-walled tubular pattern, quadrangular
Pattern disappears.
Comparative example 4
The hollow quadrangular of carbonitride of ZnO thin film is prepared according to the method for embodiment 1, unlike：Cobalt chloride is replaced respectively
It is changed to manganese chloride, nickel chloride.
Fig. 7-8 is respectively the SEM figures of manganese chloride, nickel chloride products obtained therefrom, it can be seen from the figure that products obtained therefrom is difference
The tubular morphology of form, quadrangular pattern disappear.
Comparative example 5
5.1 flow back 8 g melamines and 100 ml deionized waters at 100 DEG C, until melamine is completely dissolved, obtain
Melamine aqueous solution.
5.2 are made into iron chloride the ferric chloride in aqueous solution of a concentration of 0.1 g/ml, and 800 microlitres of ferric chloride in aqueous solution are added
Enter in melamine aqueous solution, under stiring, 100 DEG C reflux 30 min, so that melamine and iron chloride is sufficiently mixed uniformly.
5.3 after melamine and iron chloride are sufficiently mixed uniformly, directly stop heating, by 100 DEG C of solution according to 1
DEG C/rate of temperature fall of min cools down, until being down to room temperature, realize crystallization.
5.4 take out the crystal of precipitation from solution, and the solution on crystal is blotted on filter paper, obtain the trimerization of Fe2O3 doping
Cyanamide crystal.
5.5 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.
The 5.6 sample mortar grinders for obtaining calcining, obtain final products.
Fig. 9 is the SEM figures of products obtained therefrom, it can be seen from the figure that products obtained therefrom is fluffy tubular morphology, four prism type
Looks disappear.
Comparative example 6
6.1 flow back 8 g melamines and 100 ml deionized waters at 100 DEG C, until melamine is completely dissolved, obtain
Melamine aqueous solution.
6.2 are made into cobalt chloride the cobalt chloride solution of a concentration of 0.1 g/ml, and 800 microlitres of cobalt chloride solutions are added
Enter in melamine aqueous solution, under stiring, 100 DEG C reflux 30 min, so that melamine and cobalt chloride is sufficiently mixed uniformly.
Solution temperature after melamine and cobalt chloride are sufficiently mixed uniformly, are maintained 80 DEG C, keeps crystal slow by 6.3
It grows up.
6.4 take out the crystal after growing up from solution, and the solution on crystal is blotted on filter paper, obtain the three of cobalt doped
Poly cyanamid crystal.
6.5 by the melamine crystals of cobalt doped 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.
The 6.6 sample mortar grinders for obtaining calcining, obtain final products.
The SEM figures of products obtained therefrom are as shown in Figure 10, it can be seen from the figure that products obtained therefrom is the bulk morphologies of accumulation.
Claims (10)
1. a kind of hollow quadrangular of the carbonitride of ZnO thin film, it is characterized in that：The outer side bottom surface wall length of side of hollow quadrangular is
300-400nm, a length of 4-10 μm of rib, wall thickness are 20-50 nanometers.
2. the hollow quadrangular of the carbonitride of ZnO thin film according to claim 1, it is characterized in that：The hollow quadrangular
For four hollow right prisms.
3. the hollow quadrangular of the carbonitride of ZnO thin film according to claim 1 or 2, it is characterized in that：The cobalt is with two
The state of valence ion is evenly distributed on C3N4In piperazine loop network.
4. the preparation method of the hollow quadrangular of carbonitride of the ZnO thin film described in a kind of any one of claim 1-3,
It is characterized in including the following steps：
（1）Nitrogenous organic precursor, divalent cobalt and water are made into homogeneous solution；
（2）By step（1）Homogeneous solution be heated to boiling, then stop heating, the homogeneous solution of boiling is dropped in cold water
Warm crystallization；
（3）The crystal of precipitation is calcined, the hollow quadrangular of carbonitride of ZnO thin film is obtained.
5. preparation method according to claim 4, it is characterized in that：Step（1）In, it, first will be nitrogenous when preparing homogeneous solution
Organic precursor is mixed with water, is heated to reflux to nitrogenous organic precursor and is completely dissolved, and divalent cobalt is then added and is uniformly mixed,
The divalent cobalt is added in the form of solid or aqueous solution.
6. preparation method according to claim 4, it is characterized in that：Step（2）In, the homogeneous solution of boiling is directly placed into 0
DEG C ice water in cool down crystallization.
7. according to the preparation method described in claim 4,5 or 6, it is characterized in that：Step（1）In, nitrogenous organic precursor is equal
A concentration of 0.06-0.1g/mL in even solution；The mass ratio of divalent cobalt and nitrogenous organic precursor is 1 ~ 2：100.
8. according to the preparation method described in claim 4,5 or 6, it is characterized in that：Step（1）In, the nitrogenous organic precursor
For melamine or dicyandiamide, the divalent cobalt is cobalt chloride or cobalt nitrate.
9. preparation method according to claim 4, it is characterized in that：Step（3）In, calcination temperature is 550-600 DEG C, is forged
The burning time is 2-6 h.
10. the preparation method according to claim 4 or 9, it is characterized in that：Step（3）In, with the heating speed of 1-2 DEG C/min
Degree rises to 550-600 DEG C and is calcined；Calcining carries out under gas shield, and the gas is preferably nitrogen or inert gas.
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