CN107999112A - The S-C of class graphene-structured3N4Synthetic ammonia catalyst and preparation method thereof - Google Patents
The S-C of class graphene-structured3N4Synthetic ammonia catalyst and preparation method thereof Download PDFInfo
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- CN107999112A CN107999112A CN201711269056.7A CN201711269056A CN107999112A CN 107999112 A CN107999112 A CN 107999112A CN 201711269056 A CN201711269056 A CN 201711269056A CN 107999112 A CN107999112 A CN 107999112A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 25
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 235000015250 liver sausages Nutrition 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 230000029553 photosynthesis Effects 0.000 abstract 1
- 238000010672 photosynthesis Methods 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005277 cation exchange chromatography Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation method of the S C3N4 efficient visible light synthetic ammonia catalysts of the class graphene-structured of sulfur doping, comprise the following steps：Thiocarbamide and urea are mixed in a certain ratio, the mixture after uniformly mixing is placed in high temperature porcelain boat, then covers pate dure boat with porcelain boat cover board；The high temperature porcelain boat is placed in Muffle furnace, is calcined in gas atmosphere, obtains the S C3N4 catalyst of the class graphene-structured of sulfur doping.The visible photosynthesis ammonia efficiency of the S C3N4 catalyst of the class graphene-structured of the sulfur doping of preparation is higher.Under normal temperature and pressure and visible ray or direct solar radiation, it is potential and desired new way that N2 is reduced into NH3 by the S C3N4 catalyst of the class graphene-structured based on sulfur doping.
Description
Technical field
The present invention relates to photocatalytic synthesis ammonification technical field, more particularly to a kind of S- of the class graphene-structured of sulfur doping
C3N4Efficient visible light synthetic ammonia catalyst and preparation method thereof.
Background technology
The energy is the source of human society survival and development, and ammonia is one of important inorganic chemical product, ammonia synthesizing industry
Occupy critical role in national economy.With increasing for expanding economy and population, the nitrogenous fertilizer agriculturally used such as urea, nitre
Sour ammonium, ammonium phosphate, ammonium chloride and it is various contain nitrogen composite fertilizer, all using ammonia as raw material.It is large chemical products to synthesize ammonia, and the world is every
Year synthesis hydrazine yield is up to more than 100,000,000 tons, wherein about 80% is used for chemical fertilizer, 20% is used as the raw material of other chemical products.
And ammonia, it is the optimal energy as one kind cleaning, the high-energy-density energy.For the utilization of ammonia, its scale
Preparation is the basis that ammonia utilizes.The method of current ammonia processed predominantly directly synthesizes ammonia using nitrogen with hydrogen, its high temperature
The energy consumption of height compacting ammonia process is big, seriously polluted, is unfavorable for the acquisition of the ammonia energy of sustainability.And using water and nitrogen as original
It is safer by comparison that material using light-catalysed method prepares ammonia, and efficiently, environmental protection is sustainable.
Up to the present most of catalyst needed using photocatalysis production ammonia is all to synthesize system on a small scale by laboratory
For what is obtained, its primary synthetic methods has the preparation approachs such as hydro-thermal method, high-temperature calcination, vapour deposition.These methods consume energy mostly
Higher or yield is too small, can not be used on a large scale.Meanwhile nitrogen is highly stable a kind of simple substance-it is a kind of
Inert gas.Three chemical bonds (two pi bonds and a σ key) very difficult fracture of nitrogen, causes the efficiency of fixed nitrogen very low.
The content of the invention
In view of this, the technical problem to be solved in the present invention is a kind of S- for the class graphene-structured for providing sulfur doping
C3N4Efficient visible light synthetic ammonia catalyst and preparation method thereof, the S-C of the class graphene-structured of the sulfur doping of preparation3N4Have
Higher catalytic activity.
To solve problem above, the present invention provides a kind of S-C of the class graphene-structured of sulfur doping3N4Efficient visible light
The preparation method of synthetic ammonia catalyst, comprises the following steps：
Thiocarbamide and urea are mixed in a certain ratio, the mixture after uniformly mixing is placed in high temperature porcelain boat, then
Pate dure boat is covered with porcelain boat cover board；
The high temperature porcelain boat is placed in Muffle furnace, is calcined in gas atmosphere, obtains the class graphene of sulfur doping
The S-C of structure3N4Catalyst.
The thiocarbamide and the mass ratio of urea are (1~10)：1.
The mode of the mixed processing is the one or more in grinding, ball milling and mechanical agitation.
The Muffle furnace programming rate is 5~10 DEG C/min.
The calcining heat is 400~600 DEG C.
When the calcination time is that calcining 1~6 is small.
The gas atmosphere is the one or more in oxygen, air, nitrogen and argon gas.
The high temperature porcelain boat is quartz, Al2O3、Si3N4Or BN materials.
The present invention utilize high temperature confinement combustion method, is formed and is rich in nitrogen, sulphur, the atmosphere of carbon compound, allows nitrogen, sulphur, carbon activity
Material uniformly and quickly reacts, and generates the S-C of the class graphene-structured of uniform sulfur doping3N4Effective catalyst.High temperature inert
Environment promotes rapid reaction progress, while also increases active area and the catalytic reaction work of photocatalysis production ammonia catalytic reaction
Property site.
Above-mentioned preparation method provided by the invention is simple using equipment, it is only necessary to which porcelain boat and most common industrial chemicals are
It can be produced in batches, product is low for the pollution level of environment with raw material.
The S-C of the class graphene-structured of the sulfur doping prepared present invention also offers above-mentioned preparation method3N4Catalyst.
Brief description of the drawings
The diffraction pattern that Fig. 1 is obtained for sample progress XRD analysis prepared by the present invention；
Fig. 2 carries out sample prepared by the present invention adsorption-desorption curve that N2 adsorption analysis is obtained；
Fig. 3 is the ultraviolet-visible absorption spectroscopy figure of sample prepared by the present invention；
Fig. 4 is that the performance map of ammonia is produced in the photocatalysis of sample prepared by the present invention；
Embodiment
In order to further illustrate the present invention, the class graphene with reference to embodiment to a kind of sulfur doping provided by the invention
The S-C of structure3N4Efficient visible light synthetic ammonia catalyst and preparation method thereof is described in detail.
Embodiment 1：
By thiocarbamide and urea in mass ratio 1:1 ratio mixing, places the mixing after uniformly mixing in high temperature porcelain boat
Thing, then covers pate dure boat with porcelain boat cover board；The high temperature porcelain boat is placed in Muffle furnace, is forged in nitrogen atmosphere
Burn, calcining heat is 550 degrees Celsius, when calcination time is 2 small, obtains the S-C of the class graphene-structured of sulfur doping3N4Catalyst.
50 grams of obtained catalyst are weighed, is dispersed in 100mL deionized waters, nitrogen is persistently blasted into water, utilize the xenon lamp of 300W
Light source is irradiated, and was taken 3mL reaction solutions every 20 minutes, is centrifuged, and removes catalyst, and supernatant is utilized and is purchased from market
Cation chromatography product is detected, obtain the concentration of ammonium ion in aqueous solution
The sample of preparation is analyzed using XRD, the result is shown in Figure 1.As shown in Figure 1, synthesized sample is sulfur doping
Class graphene-structured S-C3N4, occur without miscellaneous peak.
Nitrogen adsorption analysis is carried out to the sample of preparation, the result is shown in Fig. 2, S-C as shown in Figure 23N4Sample has nitrogen good
Good absorption property, is conducive to the reaction of photocatalysis fixed nitrogen.
Ultraviolet-visible absorption spectroscopy analysis is carried out to the sample of preparation, the result is shown in Fig. 3, from the figure 3, it may be seen that S-C3N4Sample pair
Uv and visible light has good absorption, and effective energy source can be provided for photocatalysis.
The test of photocatalysis fixed nitrogen is carried out to the sample of preparation, the result is shown in Fig. 4, as shown in Figure 4, S-C3N4Sample has steady
Fixed efficient photocatalysis fixed nitrogen performance, efficiency be about 5 mMs per hour.
Embodiment 2：
By thiocarbamide and urea in mass ratio 1:3 ratio mixing, places the mixing after uniformly mixing in high temperature porcelain boat
Thing, then covers pate dure boat with porcelain boat cover board；The high temperature porcelain boat is placed in Muffle furnace, is forged in nitrogen atmosphere
Burn, calcining heat is 550 degrees Celsius, when calcination time is 2 small, obtains the S-C of the class graphene-structured of sulfur doping3N4Catalyst.
50 grams of obtained catalyst are weighed, is dispersed in 100mL deionized waters, nitrogen is persistently blasted into water, utilize the xenon lamp of 300W
Light source is irradiated, and was taken 3mL reaction solutions every 20 minutes, is centrifuged, and removes catalyst, and supernatant is utilized and is purchased from market
Cation chromatography product is detected, obtain the concentration of ammonium ion in aqueous solution
After testing, the sample of preparation has the catalytic activity suitable with 1 sample of embodiment.
Embodiment 3：
By thiocarbamide and urea in mass ratio 2:1 ratio mixing, places the mixing after uniformly mixing in high temperature porcelain boat
Thing, then covers pate dure boat with porcelain boat cover board；The high temperature porcelain boat is placed in Muffle furnace, is forged in nitrogen atmosphere
Burn, calcining heat is 550 degrees Celsius, when calcination time is 2 small, obtains the S-C of the class graphene-structured of sulfur doping3N4Catalyst.
50 grams of obtained catalyst are weighed, is dispersed in 100mL deionized waters, nitrogen is persistently blasted into water, utilize the xenon lamp of 300W
Light source is irradiated, and was taken 3mL reaction solutions every 20 minutes, is centrifuged, and removes catalyst, and supernatant is utilized and is purchased from market
Cation chromatography product is detected, obtain the concentration of ammonium ion in aqueous solution
After testing, the sample of preparation has the catalytic activity suitable with 1 sample of embodiment.
Embodiment 4：
By thiocarbamide and urea in mass ratio 1:5 ratio mixing, places the mixing after uniformly mixing in high temperature porcelain boat
Thing, then covers pate dure boat with porcelain boat cover board；The high temperature porcelain boat is placed in Muffle furnace, is forged in nitrogen atmosphere
Burn, calcining heat is 550 degrees Celsius, when calcination time is 2 small, obtains the S-C of the class graphene-structured of sulfur doping3N4Catalyst.
50 grams of obtained catalyst are weighed, is dispersed in 100mL deionized waters, nitrogen is persistently blasted into water, utilize the xenon lamp of 300W
Light source is irradiated, and was taken 3mL reaction solutions every 20 minutes, is centrifuged, and removes catalyst, and supernatant is utilized and is purchased from market
Cation chromatography product is detected, obtain the concentration of ammonium ion in aqueous solution
After testing, the sample of preparation has the catalytic activity suitable with 1 sample of embodiment.
Embodiment 5：
By thiocarbamide and urea in mass ratio 5:1 ratio mixing, places the mixing after uniformly mixing in high temperature porcelain boat
Thing, then covers pate dure boat with porcelain boat cover board；The high temperature porcelain boat is placed in Muffle furnace, is forged in nitrogen atmosphere
Burn, calcining heat is 550 degrees Celsius, when calcination time is 2 small, obtains the S-C of the class graphene-structured of sulfur doping3N4Catalyst.
50 grams of obtained catalyst are weighed, is dispersed in 100mL deionized waters, nitrogen is persistently blasted into water, utilize the xenon lamp of 300W
Light source is irradiated, and was taken 3mL reaction solutions every 20 minutes, is centrifuged, and removes catalyst, and supernatant is utilized and is purchased from market
Cation chromatography product is detected, obtain the concentration of ammonium ion in aqueous solution
After testing, the sample of preparation has the catalytic activity suitable with 1 sample of embodiment.
The S-C of the class graphene-structured of the sulfur doping prepared from above-described embodiment, the present invention3N4Efficient visible light closes
Ammonification catalyst has higher catalytic activity.
The explanation of above example is only intended to help to understand method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
- A kind of 1. S-C of the class graphene-structured of sulfur doping3N4The preparation method of efficient visible light synthetic ammonia catalyst, its feature It is, comprises the following steps：Thiocarbamide and urea are mixed in a certain ratio, the mixture after uniformly mixing is placed in high temperature porcelain boat, then uses porcelain Boat cover board covers pate dure boat；The high temperature porcelain boat is placed in Muffle furnace, is calcined in gas atmosphere, obtains the class graphene-structured of sulfur doping S-C3N4Catalyst.
- 2. preparation method according to claim 1, it is characterised in that the mass ratio of the thiocarbamide and urea is (1~10)： 1。
- 3. preparation method according to claim 1, it is characterised in that the mode of the mixed processing for grinding, ball milling and One or more in mechanical agitation.
- 4. preparation method according to claim 1, it is characterised in that the Muffle furnace programming rate is 5~10 DEG C/min.
- 5. preparation method according to claim 1, it is characterised in that the calcining heat is 400~600 DEG C.
- 6. preparation method according to claim 1, it is characterised in that when the calcination time is that calcining 1~6 is small.
- 7. preparation method according to claim 1, it is characterised in that the gas atmosphere is oxygen, air, nitrogen and argon One or more in gas.
- 8. preparation method according to claim 1, it is characterised in that the high temperature porcelain boat is quartz, Al2O3、Si3N4Or BN Material.
- 9. the S-C of the class graphene-structured of sulfur doping prepared by claim 1~8 any one of them preparation method3N4Catalysis Agent.
- 10. the S-C of the class graphene-structured of sulfur doping prepared by claim 1~9 any one of them preparation method3N4Catalysis Agent can be used for efficient visible light synthesis ammonia.
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| CN201711269056.7A CN107999112A (en) | 2017-12-05 | 2017-12-05 | The S-C of class graphene-structured3N4Synthetic ammonia catalyst and preparation method thereof |
| PCT/CN2018/087120 WO2019109597A1 (en) | 2017-12-05 | 2018-05-16 | Sulfur-doped s-c3n4 ammonia synthesis catalyst with graphene-like structure and preparation method therefor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019109597A1 (en) * | 2017-12-05 | 2019-06-13 | 宿州学院 | Sulfur-doped s-c3n4 ammonia synthesis catalyst with graphene-like structure and preparation method therefor |
| CN110548533A (en) * | 2019-09-11 | 2019-12-10 | 王杰 | Preparation method and application of metal and nonmetal co-doped carbon nitride nano material |
| CN116443851A (en) * | 2023-05-06 | 2023-07-18 | 大连理工大学 | Method for preparing high-nitrogen-doped carbon material by molecular scale finite field pyrolysis and application |
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| CN115055199B (en) * | 2022-05-07 | 2023-11-03 | 盐城工学院 | Sulfur-doped honeycomb nano sheet g-C 3 N 4 Preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172057A (en) * | 2013-03-07 | 2013-06-26 | 华南理工大学 | Preparation method of nitrogen and sulfur co-doped graphene |
| CN105289689A (en) * | 2015-11-07 | 2016-02-03 | 南昌航空大学 | Synthesis and application of nitrogen-doped graphene quantum dot/similar-graphene phase carbon nitride composite material |
| CN105417532A (en) * | 2015-12-22 | 2016-03-23 | 北京理工大学 | One-step preparation method for high nitrogen doped graphene |
| CN105642328A (en) * | 2014-11-11 | 2016-06-08 | 中国科学院大连化学物理研究所 | Application for nitrogen-doped graphene used as catalyst in removal of SO2 through electrooxidation method |
| CN106207204A (en) * | 2016-09-19 | 2016-12-07 | 青岛科技大学 | Nitrogen sulfur difunctional VPO catalysts of codope material with carbon element and its preparation method and application |
| US20170057821A1 (en) * | 2015-08-31 | 2017-03-02 | Institute Of Process Engineering, Chinese Academy Of Sciences | Graphitic carbon nitride material, and its synthetic method and applications |
| CN106669760A (en) * | 2016-12-28 | 2017-05-17 | 广州中国科学院沈阳自动化研究所分所 | Sulfur-doped carbon nitride photocatalyst as well as preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289181B (en) * | 2008-05-29 | 2010-09-01 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
| CN104399508B (en) * | 2014-11-20 | 2017-01-18 | 华南理工大学 | Nitrogen-sulfur co-doped carbon material with electro-catalytic oxygen reduction activity and preparation method of carbon material |
| CN104555987B (en) * | 2015-01-27 | 2016-05-25 | 齐鲁工业大学 | A kind of preparation method of nitrogen sulphur codope material with carbon element |
| CN107999112A (en) * | 2017-12-05 | 2018-05-08 | 宿州学院 | The S-C of class graphene-structured3N4Synthetic ammonia catalyst and preparation method thereof |
-
2017
- 2017-12-05 CN CN201711269056.7A patent/CN107999112A/en active Pending
-
2018
- 2018-05-16 WO PCT/CN2018/087120 patent/WO2019109597A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172057A (en) * | 2013-03-07 | 2013-06-26 | 华南理工大学 | Preparation method of nitrogen and sulfur co-doped graphene |
| CN105642328A (en) * | 2014-11-11 | 2016-06-08 | 中国科学院大连化学物理研究所 | Application for nitrogen-doped graphene used as catalyst in removal of SO2 through electrooxidation method |
| US20170057821A1 (en) * | 2015-08-31 | 2017-03-02 | Institute Of Process Engineering, Chinese Academy Of Sciences | Graphitic carbon nitride material, and its synthetic method and applications |
| CN105289689A (en) * | 2015-11-07 | 2016-02-03 | 南昌航空大学 | Synthesis and application of nitrogen-doped graphene quantum dot/similar-graphene phase carbon nitride composite material |
| CN105417532A (en) * | 2015-12-22 | 2016-03-23 | 北京理工大学 | One-step preparation method for high nitrogen doped graphene |
| CN106207204A (en) * | 2016-09-19 | 2016-12-07 | 青岛科技大学 | Nitrogen sulfur difunctional VPO catalysts of codope material with carbon element and its preparation method and application |
| CN106669760A (en) * | 2016-12-28 | 2017-05-17 | 广州中国科学院沈阳自动化研究所分所 | Sulfur-doped carbon nitride photocatalyst as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李军奇等: ""g-C3N4/ g-C3N4异质结结构的制备及其光催化性能"", 《陕西科技大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019109597A1 (en) * | 2017-12-05 | 2019-06-13 | 宿州学院 | Sulfur-doped s-c3n4 ammonia synthesis catalyst with graphene-like structure and preparation method therefor |
| CN110548533A (en) * | 2019-09-11 | 2019-12-10 | 王杰 | Preparation method and application of metal and nonmetal co-doped carbon nitride nano material |
| CN116443851A (en) * | 2023-05-06 | 2023-07-18 | 大连理工大学 | Method for preparing high-nitrogen-doped carbon material by molecular scale finite field pyrolysis and application |
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