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 PDF

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Publication number
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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preparation
structured
class graphene
catalyst
sulfur doping
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许海峰
毛强
郝保明
叶吾梅
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Suzhou University
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Suzhou University
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Priority to PCT/CN2018/087120 priority patent/WO2019109597A1/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/02Preparation, purification or separation of ammonia
    • C01C1/026Preparation of ammonia from inorganic compounds
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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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

The S-C of class graphene-structured3N4Synthetic ammonia catalyst and preparation method thereof
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)

  1. 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. 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. 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. 4. preparation method according to claim 1, it is characterised in that the Muffle furnace programming rate is 5~10 DEG C/min.
  5. 5. preparation method according to claim 1, it is characterised in that the calcining heat is 400~600 DEG C.
  6. 6. preparation method according to claim 1, it is characterised in that when the calcination time is that calcining 1~6 is small.
  7. 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. 8. preparation method according to claim 1, it is characterised in that the high temperature porcelain boat is quartz, Al2O3、Si3N4Or BN Material.
  9. 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. 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.
CN201711269056.7A 2017-12-05 2017-12-05 The S-C of class graphene-structured3N4Synthetic ammonia catalyst and preparation method thereof Pending CN107999112A (en)

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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

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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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Application publication date: 20180508