CN104607231B - There is carbon nitride photocatalyst of three-dimensional ordered macroporous structure and preparation method thereof - Google Patents
There is carbon nitride photocatalyst of three-dimensional ordered macroporous structure and preparation method thereof Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses having carbon nitride photocatalyst of three-dimensional ordered macroporous structure and preparation method thereof, carbon nitride photocatalyst has the 3-D ordered multiporous pattern of arranged regular, and macropore cavity is spherical, a diameter of 100nm～300nm；The distance of two adjacent macropore centre ofs sphere is 110nm～350nm.The scanning electron microscope diagram piece of the carbon nitride photocatalyst of the present invention shows that it has the macroporous structure of three-dimensional order, and macropore cavity is spherical, a diameter of 100nm～300nm；Macroporous structure has higher specific surface area, on the one hand can load other materials, be on the other hand easy to mass transfer in the orderly cavity of macropore, can be with sharp separation photo-generated carrier in reaction.The structure of the carbon nitride photocatalyst of the present invention has been obviously improved the photocatalysis performance of catalyst, has higher photocatalytic water H2-producing capacity under visible light, realizes efficient solar photolysis water hydrogen gas.
Description
Technical field
The invention belongs to photocatalysis technology field is and in particular to a kind of nitridation with three-dimensional ordered macroporous structure is carbon light urges
Agent and preparation method thereof.
Background technology
Conductor photocatalysis are that semiconductor catalyst produces electron-hole pair under visible ray or action of ultraviolet light, absorption
O in semiconductor surface2、H2O and contaminant molecule accept light induced electron or hole, and a series of redox reaction occurs
A kind of photochemical method.
Carbonitride is a kind of organic polymer semiconductor, because it has can be more stable in water with responding to visible light characteristic
And nontoxic, and it is easier the features such as preparation, cause the extensive concern of researcher.Carbonitride is in photocatalysis, multiphase
The fields such as catalysis, fuel cell have potential application prospect, and especially under visible light conditions, catalytic decomposition water prepares hydrogen
On, carbonitride has the advantage of the uniqueness such as efficient, nontoxic, stable.
The size of the pore structure on carbon nitride material surface and specific surface area plays highly important work on its application performance
With.At present, the common method preparing carbonitride has fusion method, soft mode version method, die version method etc., and is obtained by various technology
The nano materials such as the nanometer sheet of carbonitride, nanometer rods, nanosphere, mesoporous carbonitride are arrived.
Such as Chinese patent literature CN 103623856 A（Application number 201310663870.2）Disclose a kind of multistage receive
The spherical mesoporous carbon nitride photocatalyst of rice structure, described spherical mesoporous carbonitride has with nanometer sheet or similar nanometer sheet
Little particle equably diffuses to form, to surrounding, the micro-nano structure that surface texture highly opens wide, nanostructure height is stable from the centre of sphere.
Preparation method comprises the following steps：（1）The spherical mesoporous silicon dioxide that synthetic surface structure height is opened wide；（2）By spherical mesoporous
Silicon dioxide, after high-temperature calcination removes Organic substance, grinds, and adds dilute hydrochloric acid to carry out acid treatment under heated and stirred, and centrifugation is dried
Dry, grind；（3）In the flask containing sucking filtration head, add silicon dioxide and cyanamide, under vacuum, ultrasonic and heating；Add water
It is centrifuged off excessive cyanamide, dry；Pressed powder is calcined 2～8h in 723K～923K nitrogen furnace high temperature；Use NH4HF2Solution
Etching removes silica template, washing, dries, obtains final product spherical mesoporous carbonitride.The spherical mesoporous obtaining according to the method described above
Nitridation carbon surface has meso-hole structure, and specific surface area is larger, but synthetic method is complicated, and synthesis is relatively costly, and mesoporous hole
Footpath less it is impossible to load the larger material of other particle diameters.
Such as Chinese patent literature CN 103721745 A again（Application number 201410006468.1）Disclose a kind of copolymerization
Close modified order mesoporous carbon nitride photocatalyst, the modified order mesoporous carbonitride of described combined polymerization has the microcosmic of cylindrical bar shape
Pattern and the regular mesopore orbit of two-dimentional six side's P6mm ordered arrangement, light absorbs band edge is in 450nm～700nm.Preparation method bag
Include following steps：（1）Synthesize two-dimentional six side's P6mm SBA-15 type ordered mesoporous silica dioxides；（2）SBA-15 type order mesoporous two
Silicon oxide, after high-temperature calcination, grinding, adds dilute hydrochloric acid, centrifugation, precipitate drying while stirring in a heated condition, obtains sour
Ordered mesoporous silica dioxide after change；（3）Ordered mesoporous silica dioxide after cyanamide, 3- aminothiophene -2- formonitrile HCN and acidifying mixes
Close, ultrasonic in a heated condition and evacuation；Add water centrifugation, is dried, in 450 DEG C～650 DEG C nitrogen furnace high temperature thermopolymerizations 2～8
Hour；Remove silica template with ammonium hydrogen fluoride solution, washing, it is dried, obtain final product the modified order mesoporous carbonitride of combined polymerization.
Likewise, the modified order mesoporous carbonitride synthetic method of the combined polymerization disclosed in this patent documentation is complicated, relatively costly, mesoporous
Duct size is difficult to adjust it is impossible to load the larger material of other particle diameters.
Content of the invention
The technical problem to be solved is to provide a kind of carbonitride photocatalysis with three-dimensional ordered macroporous structure
Agent and preparation method thereof.
The technical scheme realizing an object of the present disclosure is a kind of carbonitride photocatalysis with three-dimensional ordered macroporous structure
Agent, has the 3-D ordered multiporous pattern of arranged regular, and macropore cavity is spherical, a diameter of 100nm～300nm；Adjacent two
The distance of the individual macropore centre of sphere is 110nm～350nm.
The technical scheme realizing the present invention second purpose is a kind of carbonitride photocatalysis with three-dimensional ordered macroporous structure
The preparation method of agent, comprises the following steps：
1. prepare the silica spheres array mould plate of three-dimensional order；Ethanol, water, ammonia mixing and stirring are mixed
Solution；Add tetraethyl orthosilicate in mixed solution, after stirring 3～4 hours, the material that will obtain after reacting is centrifuged, and removes
Centrifuge mother liquor, is centrifuged the precipitation washing with alcohol obtaining, and dries and obtains silica spheres；Ethanol, water, ammonia, positive silicic acid tetrem
The mass ratio of ester is 50:（5～18）∶（2～6）∶（3～8）.
By silica spheres ultrasonic disperse obtained above in ethanol, the suspension surface obtaining after ultrasonic disperse is covered
Lid thin film, standing, treat that suspension evaporates into dry, the silicon dioxide ball array mould that the white solid obtaining arranges for three-dimensional order
Plate.
2. there is the preparation of the carbon nitride photocatalyst of three-dimensional ordered macroporous structure；1. in the white solid obtaining to step
Add cyanamide to obtain solidliquid mixture, then solidliquid mixture is sent in vacuum drying oven, by evacuation in vacuum drying oven,
The temperature inside the box is warming up to 55 DEG C～70 DEG C, standing was taken out after 2～4 hours, obtains white solid, be intermediate A after cooling；Its
The white solid that 1. middle step obtains is 1: 1～3 with the mass ratio of cyanamide.
The intermediate A obtaining is put in tube furnace, under nitrogen protection, at 520 DEG C～550 DEG C, holding 2～4 is little
When, obtain yellow powder after cooling, be intermediate B.
Intermediate B is transferred in HF solution, stirring was centrifuged after 4～8 hours, and the precipitation being centrifugally separating to obtain washes with water
Wash, after drying, obtain final product the carbon nitride photocatalyst with three-dimensional ordered macroporous structure.
As preferred, 1. middle ethanol, water, ammonia, the mass ratio of tetraethyl orthosilicate are 50 to above-mentioned steps:（5～
15）∶（2～5）∶（3～6）.
As it is further preferred that above-mentioned steps 1. middle ethanol, water, ammonia, tetraethyl orthosilicate mass ratio be 50:
（5～10）∶（2～4）∶（3～6）.
In the suspension that 1. above-mentioned steps obtain after middle ultrasonic disperse, the concentration of silica spheres is 25～50g/L
The second technical scheme realizing the present invention second purpose is a kind of carbonitride with three-dimensional ordered macroporous structure
The preparation method of photocatalyst, comprises the following steps：
1. prepare the silica spheres array mould plate of three-dimensional order；Ethanol, water, ammonia mixing and stirring are mixed
Solution；Add tetraethyl orthosilicate in mixed solution, after stirring 3～4 hours, the material that will obtain after reacting is centrifuged, and removes
Centrifuge mother liquor, is centrifuged the precipitation washing with alcohol obtaining, and dries and obtains silica spheres；Ethanol, water, ammonia, positive silicic acid tetrem
The mass ratio of ester is 50:（5～18）∶（2～6）∶（3～8）.
By silica spheres ultrasonic disperse obtained above in ethanol, by the suspension obtaining after ultrasonic disperse with
The speed high speed centrifugation of 8000r/min～10000r/min, discards the silicon dioxide spherical array that ethanol post-drying obtains three-dimensional order
Row template.
2. there is the preparation of the carbon nitride photocatalyst of three-dimensional ordered macroporous structure；1. in the white solid obtaining to step
Add cyanamide to obtain solidliquid mixture, then solidliquid mixture is sent in vacuum drying oven, by evacuation in vacuum drying oven,
The temperature inside the box is warming up to 55 DEG C～70 DEG C, standing was taken out after 2～4 hours, obtains white solid, be intermediate A after cooling；Its
The white solid that 1. middle step obtains is 1: 1～3 with the mass ratio of cyanamide.
The intermediate A obtaining is put in tube furnace, under nitrogen protection, keeps 2～4 hours at 520～550 DEG C,
Obtain yellow powder after cooling, be intermediate B.
Intermediate B is transferred in HF solution, stirring was centrifuged after 4～8 hours, and the precipitation being centrifugally separating to obtain washes with water
Wash, after drying, obtain final product the carbon nitride photocatalyst with three-dimensional ordered macroporous structure.
As preferred, 1. middle ethanol, water, ammonia, the mass ratio of tetraethyl orthosilicate are 50 to above-mentioned steps:（5～
15）∶（2～5）∶（3～6）.
As it is further preferred that above-mentioned steps 1. middle ethanol, water, ammonia, tetraethyl orthosilicate mass ratio be 50:
（5～10）∶（2～4）∶（3～6）.
In the suspension that 1. above-mentioned steps obtain after middle ultrasonic disperse, the concentration of silica spheres is 80～120g/L.
The present invention has positive effect：（1）The scanning electron microscope diagram piece of the carbon nitride photocatalyst of the present invention shows
Show that its microscopic appearance has the macroporous structure of three-dimensional order, macropore cavity is spherical, a diameter of 100nm～300nm；Macroporous structure
There is higher specific surface area, on the one hand can load other materials in the orderly cavity of macropore, on the other hand be easy to mass transfer,
Can be with sharp separation photo-generated carrier in reaction.The structure of the carbon nitride photocatalyst of the present invention has been obviously improved the light of catalyst
Catalytic performance, has higher photocatalytic water H2-producing capacity under visible light, realizes efficient solar photolysis water hydrogen gas.
（2）The preparation method of the carbon nitride photocatalyst of the present invention prepares the silicon dioxide of three-dimensional order arrangement first
Ball, then using the three-dimensional ordered array of silica spheres as masterplate, with cyanamide as predecessor, gathers in protective gas high temperature
Close, finally removed with Fluohydric acid. and the carbon nitride photocatalyst with three-dimensional ordered macroporous structure after silicon dioxide, is obtained.
（3）The size of the macropore diameter of the carbon nitride photocatalyst of the present invention is passed through to control silicon dioxide in preparation process
The size of ball can very easily be adjusted so that carbon nitride photocatalyst is suitable for loading different size of other materials.When
When needing the volume of the other materials of load larger, prepare the titanium dioxide of greater particle size during preparation carbon nitride photocatalyst first
Silicon ball, is finally removed after silica spheres with Fluohydric acid., prepared catalyst has the macropore of larger aperture, and meeting application will
Ask.
（4）The catalyst of the present invention prepare that synthesis technique is simple, stability is high, and the raw material of use is inexpensive.Prepared nitrogen
Change carbon light catalyst and do not contain metal, nontoxic, can recycle, there is good practical value, have very well in photocatalysis field
Application prospect.
Brief description
Fig. 1 is 5000 times of scanning electron microscope diagram pieces of the carbon nitride photocatalyst of embodiment 1 preparation；
Fig. 2 is 20000 times of scanning electron microscope diagram pieces of the carbon nitride photocatalyst of embodiment 1 preparation；
Fig. 3 is the X-ray diffractogram of the carbon nitride photocatalyst of embodiment 1 preparation, and vertical coordinate intensity- is strong in figure
Degree, in figure abscissa degree- degree.
Fig. 4 is the photocatalysis Decomposition Aquatic product hydrogen with common carbon nitride catalyst for the carbon nitride photocatalyst of embodiment 1 preparation
Performance comparision figure, vertical coordinate be hydrogen-producing speed.
Specific embodiment
（Embodiment 1）
The carbon nitride photocatalyst with three-dimensional ordered macroporous structure of the present embodiment is a kind of organic polymer semiconductor
Photocatalyst, chemical formula is C3N4, preparation method comprises the following steps：
1. prepare the silica spheres array mould plate of three-dimensional order.
By 60g ethanol, 12g water, 4g ammonia（28wt%）Mixing and stirring obtains mixed solution；Add in mixed solution
Enter 6mL tetraethyl orthosilicate（CAS NO. 78-10-4）, stirring 3 hours after, will reaction after obtain material centrifugation, remove from
Heart mother solution, is centrifuged the precipitation washing with alcohol that obtains, then dries at 80 DEG C and obtains silica spheres.
By silica spheres ultrasonic disperse obtained above in 80mL ethanol, the suspension table that obtains after ultrasonic disperse
Face cover film, standing, treat that suspension slowly evaporates into dry, the silica spheres that the white solid obtaining arranges for three-dimensional order
Array mould plate；Wherein in suspension, the concentration of silica spheres is 25～50g/L.
2. there is the preparation of the carbon nitride photocatalyst of three-dimensional ordered macroporous structure.
1. add 2g cyanamide to obtain solidliquid mixture in the white solid obtaining to step, then solidliquid mixture is sent into
In vacuum drying oven, the temperature inside the box is warming up to 60 DEG C by evacuation in vacuum drying oven, standing was taken out after 4 hours, after cooling
Obtain white solid, be intermediate A；In intermediate A, cyanamide is sufficiently submerged in the silicon dioxide ball array masterplate of three-dimensional order arrangement.
The intermediate A obtaining is put in tube furnace, under nitrogen protection, is warming up to 550 DEG C with the speed of 4 DEG C/min,
Keep 4 hours, obtain yellow powder after cooling, be intermediate B.
Intermediate B is transferred to the HF solution of 10mL（16wt%）In, it is centrifuged after stirring 8h, the precipitation being centrifugally separating to obtain
Wash with water 3 times, after drying, obtain the carbon nitride photocatalyst of the powder with three-dimensional ordered macroporous structure.
The carbon nitride photocatalyst outward appearance with three-dimensional ordered macroporous structure manufactured in the present embodiment is pale yellow powder.
Product composition is characterized in D8-XRD type（German BRUKER company produces）Complete on X-ray diffractometer, Cu target KαSpoke
Penetrate（λ=0.154056nm）, 1.0 °/min of scanning speed, 0～80 ° of wide-angle diffraction measurement range.
The observation of pattern and granularity is in S-3400NII type（Japanese Hitachi company produces）Scanning electron microscope（SEM）
Under carry out.
See Fig. 1 and Fig. 2, scanning electron microscope diagram piece shows, the carbon nitride photocatalyst that the present embodiment is obtained has greatly
The 3-D ordered multiporous pattern of area arranged regular, macropore cavity is spherical, a diameter of 250nm～280nm.Adjacent macropore ball
The distance of the heart is 260nm～300nm.
See Fig. 3, what the XRD diffraction pattern of carbon nitride photocatalyst manufactured in the present embodiment confirmed that the present embodiment prepares is
The carbonitride of graphite-phase.
In order to check the carbon nitride photocatalyst photocatalysis Decomposition with three-dimensional ordered macroporous structure manufactured in the present embodiment
The performance of Aquatic product hydrogen, carries out photocatalytic degradation water test to it：Obtained carbon nitride photocatalyst is added 100mL water
In, the concentration of carbon nitride photocatalyst is 1*10-3g/mL；Under visible light illumination, photolysis water hydrogen；With online gas chromatogram skill
Art carries out quantitative analyses to hydrogen output.
Test as a comparison, add common body phase carbonitride to compare in 100mL water, body phase carbon nitride photocatalyst
Concentration is 1*10-3g/mL；Under visible light illumination, photolysis water hydrogen；With online gas chromatographic technique, quantitation is carried out to hydrogen output
Analysis.
Result is as shown in Figure 4：The carbon nitride photocatalyst with three-dimensional ordered macroporous structure that the present embodiment is obtained（Fig. 4
In referred to as three-dimensional ordered macroporous carbonitride）Hydrogen-producing speed is 142 μm of ol/h, and common body phase carbonitride hydrogen-producing speed is 7.8 μ
Mol/h, the H2-producing capacity of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure that the present embodiment is obtained is far above commonly
Body phase carbonitride, is 18 times of its hydrogen-producing speed.
（Embodiment 2）
The preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure of the present embodiment remaining and embodiment
Identical, difference is：
When 1. step prepares the silica spheres array mould plate of three-dimensional order, by 50g ethanol, 10g water, 3g ammonia（28
wt%%）Mixing and stirring obtains mixed solution, adds 5mL tetraethyl orthosilicate in the mixed solution obtaining, and stirs 4 hours
Afterwards, the material centrifugation that will obtain after reaction, removes centrifuge mother liquor, is centrifuged the precipitation washing with alcohol that obtains, then dries at 80 DEG C
Dry obtain silica spheres.
By the silica spheres obtaining ultrasonic disperse in 8mL ethanol, the suspension obtaining is with the speed of 10000r/min
High speed centrifugation, discards the silica spheres array mould plate that ethanol post-drying obtains three-dimensional order；Silica spheres in suspension
Concentration is 80～120g/L.
Add 2.5g cyanamide to obtain solidliquid mixture in the white solid that 1. 2. step obtain to step, then solid-liquid is mixed
Compound is sent in vacuum drying oven, and the temperature inside the box is warming up to 70 DEG C by evacuation in vacuum drying oven, and standing took after 4 hours
Go out.
The intermediate B obtaining is transferred to the HF solution of 8mL（16wt%）In, it is centrifuged after stirring 7h, be centrifugally separating to obtain is heavy
Shallow lake washes with water 3 times, obtains final product the carbon nitride photocatalyst with three-dimensional ordered macroporous structure after drying.
The carbon nitride photocatalyst that the present embodiment is obtained has the 3-D ordered multiporous pattern of large area arranged regular, macropore
Cavity is spherical, a diameter of 200nm～250nm.The distance of two adjacent macropore centre ofs sphere is 210nm～260nm.
The carbon nitride photocatalyst with three-dimensional ordered macroporous structure being obtained according to the method for embodiment 1, the present embodiment
Hydrogen-producing speed is 157 μm of ol/h.
（Embodiment 3）
The preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure of the present embodiment remaining and embodiment
Identical, difference is：
When 1. step prepares the silica spheres array mould plate of three-dimensional order, by 50g ethanol, 15 g water, 5g ammonia
（28wt%%）Mixing and stirring obtains mixed solution, adds 5mL tetraethyl orthosilicate in the mixed solution obtaining.
The carbon nitride photocatalyst that the present embodiment is obtained has the 3-D ordered multiporous pattern of large area arranged regular, macropore
Cavity is spherical, a diameter of 120nm～150nm.The distance of two adjacent macropore centre ofs sphere is 130nm～160nm.
The carbon nitride photocatalyst with three-dimensional ordered macroporous structure being obtained according to the method for embodiment 1, the present embodiment
Hydrogen-producing speed is 160 μm of ol/h.
The scanning electron microscope diagram piece of the carbon nitride photocatalyst of the present invention shows that it has the macropore of three-dimensional order knot
Structure, macropore cavity is spherical, a diameter of 100nm～300nm；Macroporous structure has a higher specific surface area, orderly macropore
On the one hand other materials can be loaded in cavity, on the other hand be easy to mass transfer, can be with sharp separation photo-generated carrier in reaction.This
The structure of the carbon nitride photocatalyst of invention has been obviously improved the photocatalysis performance of catalyst, has higher light under visible light
Solution water H2-producing capacity, realizes efficient solar photolysis water hydrogen gas.
Claims (8)
1. a kind of preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure is it is characterised in that preparation method bag
Include following steps：
1. prepare the silica spheres array mould plate of three-dimensional order；Ethanol, water, ammonia mixing and stirring are obtained mixing molten
Liquid；To in mixed solution add tetraethyl orthosilicate, stirring 3～4 hours after, will reaction after obtain material centrifugation, remove from
Heart mother solution, is centrifuged the precipitation washing with alcohol obtaining, and dries and obtains silica spheres；Ethanol, water, ammonia, tetraethyl orthosilicate
Mass ratio be 50:（5～18）∶（2～6）∶（3～8）；
By silica spheres ultrasonic disperse obtained above in ethanol, the suspension surface obtaining after ultrasonic disperse covers thin
Film, standing, treat that suspension slowly evaporates into dry, the silicon dioxide ball array mould that the white solid obtaining arranges for three-dimensional order
Plate；
2. there is the preparation of the carbon nitride photocatalyst of three-dimensional ordered macroporous structure；1. add in the white solid obtaining to step
Cyanamide obtains solidliquid mixture, then sends in vacuum drying oven by solidliquid mixture, by evacuation in vacuum drying oven, by case
Interior temperature is warming up to 55 DEG C～70 DEG C, and standing was taken out after 2～4 hours, obtains white solid, be intermediate A after cooling；Wherein walk
The rapid white solid 1. obtaining is 1: 1～3 with the mass ratio of cyanamide；
The intermediate A obtaining is put in tube furnace, under nitrogen protection, keeps 2～4 hours at 520 DEG C～550 DEG C, cold
But obtain yellow powder afterwards, be intermediate B；
Intermediate B is transferred in HF solution, stirring was centrifuged after 4～8 hours, and the precipitation being centrifugally separating to obtain washes with water, dried
The carbon nitride photocatalyst with three-dimensional ordered macroporous structure is obtained final product after dry.
2. the preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure according to claim 1, it is special
Levy and be：1. middle ethanol, water, ammonia, the mass ratio of tetraethyl orthosilicate are 50 to step:（5～15）∶（2～5）∶（3～6）.
3. the preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure according to claim 2, it is special
Levy and be：1. middle ethanol, water, ammonia, the mass ratio of tetraethyl orthosilicate are 50 to step:（5～10）∶（2～4）∶（3～6）.
4. the preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure according to claim 1, it is special
Levy and be：In the suspension that 1. step obtains after middle ultrasonic disperse, the concentration of silica spheres is 25～50g/L.
5. a kind of preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure is it is characterised in that preparation method bag
Include following steps：
1. prepare the silica spheres array mould plate of three-dimensional order；Ethanol, water, ammonia mixing and stirring are obtained mixing molten
Liquid；To in mixed solution add tetraethyl orthosilicate, stirring 3～4 hours after, will reaction after obtain material centrifugation, remove from
Heart mother solution, is centrifuged the precipitation washing with alcohol obtaining, and dries and obtains silica spheres；Ethanol, water, ammonia, tetraethyl orthosilicate
Mass ratio be 50:（5～18）∶（2～6）∶（3～8）；
By silica spheres ultrasonic disperse obtained above in ethanol, by the suspension obtaining after ultrasonic disperse with 8000r/
The speed high speed centrifugation of min～10000r/min, discards the silica spheres array mould plate that ethanol post-drying obtains three-dimensional order；
2. there is the preparation of the carbon nitride photocatalyst of three-dimensional ordered macroporous structure；1. add in the white solid obtaining to step
Cyanamide obtains solidliquid mixture, then sends in vacuum drying oven by solidliquid mixture, by evacuation in vacuum drying oven, by case
Interior temperature is warming up to 55 DEG C～70 DEG C, and standing was taken out after 2～4 hours, obtains white solid, be intermediate A after cooling；Wherein walk
The rapid white solid 1. obtaining is 1: 1～3 with the mass ratio of cyanamide；
The intermediate A obtaining is put in tube furnace, under nitrogen protection, keeps 2～4 hours at 520～550 DEG C, cooling
After obtain yellow powder, be intermediate B；
Intermediate B is transferred in HF solution, stirring was centrifuged after 4～8 hours, and the precipitation being centrifugally separating to obtain washes with water, dried
The carbon nitride photocatalyst with three-dimensional ordered macroporous structure is obtained final product after dry.
6. the preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure according to claim 5, it is special
Levy and be：1. middle ethanol, water, ammonia, the mass ratio of tetraethyl orthosilicate are 50 to step:（5～15）∶（2～5）∶（3～6）.
7. the preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure according to claim 6, it is special
Levy and be：1. middle ethanol, water, ammonia, the mass ratio of tetraethyl orthosilicate are 50 to step:（5～10）∶（2～4）∶（3～6）.
8. the preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure according to claim 5, it is special
Levy and be：In the suspension that 1. step obtains after middle ultrasonic disperse, the concentration of silica spheres is 80～120g/L.
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| CN201611136211.3A CN106732723A (en) | 2015-02-16 | 2015-02-16 | The preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure |
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| CN105126895B (en) * | 2015-09-18 | 2017-08-25 | 清华大学深圳研究生院 | Graphite phase carbon nitride sheet layer material and preparation method thereof |
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| CN106391086A (en) * | 2016-09-29 | 2017-02-15 | 中国地质大学（北京） | Preparation method of C3N4/SiO2 heterojunction photocatalyst |
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| CN109261203B (en) * | 2018-09-28 | 2021-08-31 | 福州大学 | Covalent triazine organic polymer photocatalyst capable of efficiently producing methane, and preparation and application thereof |
| CN109261191B (en) * | 2018-11-06 | 2021-07-20 | 武汉科技大学 | Graphite phase carbon nitride foam photocatalytic material and preparation method thereof |
| CN110721710B (en) * | 2019-10-21 | 2021-06-08 | 大连理工大学 | Ordered macroporous non-metal catalyst and preparation method thereof |
| CN111135850A (en) * | 2020-01-17 | 2020-05-12 | 福州大学 | Application of three-dimensional ordered macroporous carbon nitride supported palladium catalyst in catalytic hydrogenation of styrene unsaturated copolymer |
| CN111514921B (en) * | 2020-05-29 | 2022-05-31 | 上海交通大学 | Bicontinuous-structure mesoporous graphitized carbon nitride and preparation method and application thereof |
| CN114452989A (en) * | 2022-01-30 | 2022-05-10 | 江苏大学 | Porous structure carbon nitride composite catalyst and preparation method and application thereof |
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