CN106732720A - A kind of graphite phase carbon nitride compound photochemical catalyst and preparation method thereof - Google Patents
A kind of graphite phase carbon nitride compound photochemical catalyst and preparation method thereof Download PDFInfo
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- CN106732720A CN106732720A CN201611103718.9A CN201611103718A CN106732720A CN 106732720 A CN106732720 A CN 106732720A CN 201611103718 A CN201611103718 A CN 201611103718A CN 106732720 A CN106732720 A CN 106732720A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 130
- 239000010439 graphite Substances 0.000 title claims abstract description 130
- -1 carbon nitride compound Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title claims abstract description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 111
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000005864 Sulphur Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 235000011837 pasties Nutrition 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 19
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a kind of preparation method of graphite phase carbon nitride compound, graphite phase carbon nitride is mixed with the concentrated sulfuric acid, heat and stir, graphite phase carbon nitride is set to be dissolved completely in the concentrated sulfuric acid, trithiocyanuric acid is added in the concentrated sulfuric acid solution for obtain graphite phase carbon nitride, poor solvent is added after being sufficiently mixed, divide isolated precipitation and be dried, the sample that will be dried to obtain is placed in inert atmosphere and calcines, the compound being made up of graphite phase carbon nitride and sulphur regulation and control graphite phase carbon nitride is obtained, the compound can be used as photochemical catalyst.The present invention can effectively improve the mixing uniformity of graphite phase carbon nitride compound, so as to further improve the separative efficiency of its photo-generated carrier, extend application of the graphite phase carbon nitride in photocatalysis.
Description
Technical field
The present invention relates to photocatalyst technology field, and in particular to a kind of carbon nitride photocatalyst and preparation method thereof.
Background technology
Today's society, energy and environment problem becomes increasingly conspicuous, and the traditional energy such as oil, coal is non-renewable energy resources, its storage
Amount is gradually reduced, and the development and utilization of new energy turns into and enjoys today's society focus of attention.Solar energy takes as one kind
Clean energy resource not to the utmost, nexhaustible, increasingly obtain the attention of researcher, wherein, crucial using solar energy exists
In preparing efficient photochemical catalyst.
Graphite phase carbon nitride is a kind of non-metal semiconductive, and band gap is about 2.7eV so that it has certain suction to visible ray
Receipts ability, and graphite phase carbon nitride energy band covers the oxidation-reduction potential of water so that and water oxygen can be both melted into oxygen by it
Water can also be reduced into hydrogen.In addition, graphite phase carbon nitride is due to antiacid, alkali, photoetch, good stability, structure and performance
It is easy to regulation and control, with preferable photocatalysis performance, thus the study hotspot as photocatalysis field.However, single graphite-phase
Carbonitride electronics is high with hole-recombination rate, in order to solve this problem, various countries researchers it is general by graphite phase carbon nitride and its
He is made compound by semiconductor.But, graphite phase carbon nitride is difficult to dissolve, and existing method cannot be by stone when compound is formed
Black phase carbon nitride is well mixed with other semiconductors, limits the raising of photocatalysis performance.The present invention uses concentrated sulfuric acid dissolution stone
Black phase carbon nitride so that graphite phase carbon nitride can mix on a molecular scale with other semiconductors, improves graphite-phase nitridation
The mixing uniformity of carbon complex, and the graphite phase carbon nitride that will be dissolved and trithiocyanuric acid reaction, form graphite-phase nitrogen
Change the compound that carbon is constituted with sulphur regulation and control graphite phase carbon nitride, so as to further improve its photocatalysis performance.
The content of the invention
Goal of the invention：The purpose of the present invention is to solve the shortcomings of the prior art, there is provided a kind of graphite phase carbon nitride is combined
The preparation method of thing, obtains the graphite phase carbon nitride compound being well mixed from molecular level, further improves its photocatalysis
Performance.
Technical scheme：To achieve these goals, one aspect of the present invention is compound there is provided a kind of graphite phase carbon nitride
The preparation method of thing, comprises the following steps：
(1) graphite phase carbon nitride is mixed with the concentrated sulfuric acid, heats and stir, graphite phase carbon nitride is dissolved completely in dense sulphur
In acid, the concentrated sulfuric acid solution of graphite phase carbon nitride is obtained；
(2) trithiocyanuric acid is added in the concentrated sulfuric acid solution of graphite phase carbon nitride obtained in step (1), after being sufficiently mixed
Poor solvent is added, point isolated precipitation is simultaneously dried；
(3) sample that step (2) is dried to obtain is placed in inert atmosphere, during 400-600 DEG C of calcining 1-3, that is, obtains stone
Black phase carbon nitride regulates and controls graphite phase carbon nitride compound with sulphur.
In calcination process, concentrated sulfuric acid solution and the trithiocyanuric acid of graphite phase carbon nitride react, due to trithiocyanuric acid
On C atoms there is electrophilicity, reaction bonded can be carried out with the amino on graphite phase carbon nitride surface together with, then in high temperature
Lower trithiocyanuric acid can occur hot polymerization and react to form sulphur regulation and control graphite phase carbon nitride, ultimately form graphite phase carbon nitride and regulate and control with sulphur
Graphite phase carbon nitride compound.The graphite phase carbon nitride of sulphur regulation and control is prepared by the reaction of trithiocyanuric acid high temperature thermopolymerization
, the physicochemical properties and the structure of matter of the graphite phase carbon nitride of sulphur regulation and control are much like with graphite phase carbon nitride, and difference exists
In offseting downward 0.2V relative to its conduction band of graphite phase carbon nitride and valence band, and specific surface area is bigger.
For the ease of the abundant dissolving of graphite phase carbon nitride, the heating-up temperature in step (1) is set to 60~300 DEG C；
Make in the concentrated sulfuric acid solution of graphite phase carbon nitride, the concentration of graphite phase carbon nitride is 50mg/ml~200mg/ml.Graphite-phase is nitrogenized
The concentrated sulfuric acid solution of carbon is yellow, and the concentration of carbonitride is bigger, and solution colour is deeper.
In order to obtain preferable photocatalysis performance, trithiocyanuric acid addition in regulating step (2) makes to be obtained in step (3)
To compound in, carbonitride and sulphur regulation and control carbonitride ratio be 1:99—1:4.
In order that trithiocyanuric acid powder is well mixed with graphite phase carbon nitride, in step (2), by graphite phase carbon nitride
The mixture of concentrated sulfuric acid solution and trithiocyanuric acid stir into pasty state；In view of the molten of graphite phase carbon nitride and trithiocyanuric acid
Xie Xing, i.e., they are all water insoluble, so using secondary water as poor solvent.
In step (3), using nitrogen atmosphere as the inert atmosphere calcined.
Another aspect of the present invention provide a kind of graphite phase carbon nitride compound, the graphite phase carbon nitride compound by
Above-mentioned preparation method is obtained.
An additional aspect of the present invention provides a kind of photochemical catalyst, and the photochemical catalyst is compound for above-mentioned graphite phase carbon nitride
Thing.
Beneficial effect：Compared with prior art, the present invention has advantages below：The present invention utilizes concentrated sulfuric acid dissolution graphite-phase
The method of carbonitride prepares the compound that its homogeneous compound, i.e. graphite phase carbon nitride and sulphur regulate and control graphite phase carbon nitride, can be with
The mixing uniformity of the two is effectively improved, so as to further improve the separative efficiency of its photo-generated carrier；Meanwhile, the present invention will
Reacted with trithiocyanuric acid with the concentrated sulfuric acid fully lysed graphite phase carbon nitride, form graphite phase carbon nitride and regulate and control graphite with sulphur
Phase carbon nitride mixed uniformly compound on a molecular scale, effectively improves the separative efficiency of its light induced electron and hole,
So that its photocatalysis performance is improved so that application of the graphite phase carbon nitride in photocatalysis is extended.
Brief description of the drawings：
Fig. 1 is that the graphite phase carbon nitride of different proportion and sulphur regulate and control wavelength X of the graphite phase carbon nitride compound in light>
During 420nm, the speed of Photocatalyzed Hydrogen Production；
Fig. 2 is electron-hole in the compound that graphite phase carbon nitride (CN) is constituted with sulphur regulation and control graphite phase carbon nitride (CNS)
Separation principle.
Specific embodiment：
Embodiment 1
Concentrated sulfuric acid dissolution graphite phase carbon nitride：Take 0.5g graphite phase carbon nitrides to be added in the round-bottomed flask of 25ml, then
The concentrated sulfuric acid of 10ml is added, oil bath is heated with stirring to 100 DEG C, heats 1h, treat that graphite phase carbon nitride all dissolves, be cooled to room
Temperature, it is the concentrated sulfuric acid solution of the graphite phase carbon nitride of 50mg/ml to obtain the concentration of graphite phase carbon nitride.
Graphite phase carbon nitride is mixed：The concentrated sulfuric acid solution for taking 2ml graphite phase carbon nitrides adds the polysulfides of 1.2g tri- to it
Cyanic acid, so that sulphur regulation and control graphite phase carbon nitride and graphite phase carbon nitride ratio are 1 in the compound for finally giving:99, will obtain
Mixture glass bar stir into pasty state, be subsequently adding the secondary water of 30ml, use magnetic stirrer 30min, stand 1h,
Reusing Buchner funnel carries out suction filtration, then by sample drying.
Calcining：The sample that will be dried to obtain is put into the ceramic crucible of 10ml, is forged in the tube furnace being placed under nitrogen atmosphere
Burn, 400 DEG C are warming up to the speed of 4.2 DEG C/min, 3h is incubated at 400 DEG C, that is, obtain graphitiferous phase carbon nitride and sulphur regulation and control stone
The nitridation carbon complex of black phase carbon nitride, is designated as CN-CNS-0.01.
Embodiment 2
Concentrated sulfuric acid dissolution graphite phase carbon nitride：Take 1g graphite phase carbon nitrides to be added in the round-bottomed flask of 25ml, then add
Enter the concentrated sulfuric acid of 10ml, oil bath is heated with stirring to 60 DEG C, heats 1h, treat that graphite phase carbon nitride all dissolves, be cooled to room temperature, obtain
Concentration to graphite phase carbon nitride is the concentrated sulfuric acid solution of the graphite phase carbon nitride of 100mg/ml.
Graphite phase carbon nitride is mixed：The concentrated sulfuric acid solution for taking 1ml graphite phase carbon nitrides adds the polysulfides of 1.8g tri- to it
Cyanic acid, so that sulphur regulation and control carbonitride and carbonitride ratio are 1 in the compound for finally giving:9, the mixture glass that will be obtained
Rod stirs into pasty state, is subsequently adding the secondary water of 30ml, uses magnetic stirrer 30min, stands 1h, reuses Buchner funnel
Suction filtration is carried out, then by sample drying.
Calcining：The sample that will be dried to obtain is put into the ceramic crucible of 10ml, is forged in the tube furnace being placed under nitrogen atmosphere
Burn, 600 DEG C are warming up to the speed of 5 DEG C/min, 2h is incubated at 600 DEG C, that is, obtain graphitiferous phase carbon nitride and sulphur regulation and control graphite
The nitridation carbon complex of phase carbon nitride, is designated as CN-CNS-0.1.
Embodiment 3
Concentrated sulfuric acid dissolution graphite phase carbon nitride：Take 1g graphite phase carbon nitrides to be added in the round-bottomed flask of 25ml, then add
Enter the concentrated sulfuric acid of 10ml, oil bath is heated with stirring to 150 DEG C, heats 1h, treat that graphite phase carbon nitride all dissolves, be cooled to room temperature,
It is the concentrated sulfuric acid solution of the graphite phase carbon nitride of 100mg/ml to obtain the concentration of graphite phase carbon nitride.
Graphite phase carbon nitride is mixed：The concentrated sulfuric acid solution for taking 1ml graphite phase carbon nitrides adds the polysulfides of 2.4g tri- to it
Cyanic acid, so that sulphur regulation and control carbonitride and carbonitride ratio are 1 in the compound for finally giving:5, the mixture glass that will be obtained
Rod stirs into pasty state, is subsequently adding the secondary water of 30ml, uses magnetic stirrer 30min, stands 1h, reuses Buchner funnel
Suction filtration is carried out, then by sample drying.
Calcining：The sample that will be dried to obtain is put into the ceramic crucible of 10ml, is forged in the tube furnace being placed under nitrogen atmosphere
Burn, 500 DEG C are warming up to the speed of 10 DEG C/min, 2.5h is incubated at 500 DEG C, that is, obtain graphitiferous phase carbon nitride and sulphur regulation and control stone
The nitridation carbon complex of black phase carbon nitride, is designated as CN-CNS-0.2.
Embodiment 4
Concentrated sulfuric acid dissolution graphite phase carbon nitride：Take 2g graphite phase carbon nitrides to be added in the round-bottomed flask of 25ml, then add
Enter the concentrated sulfuric acid of 10ml, oil bath is heated with stirring to 200 DEG C, heats 1h, treat that graphite phase carbon nitride all dissolves, be cooled to room temperature,
It is the concentrated sulfuric acid solution of the graphite phase carbon nitride of 200mg/ml to obtain the concentration of graphite phase carbon nitride.
Graphite phase carbon nitride is mixed：The concentrated sulfuric acid solution for taking 0.5ml graphite phase carbon nitrides adds the polysulfides of 3g tri- to it
Cyanic acid, so that sulphur regulation and control carbonitride and carbonitride ratio are 1 in the compound for finally giving:4, the mixture glass that will be obtained
Rod stirs into pasty state, is subsequently adding the secondary water of 30ml, uses magnetic stirrer 30min, stands 1h, reuses Buchner funnel
Suction filtration is carried out, then by sample drying.
Calcining：The sample that will be dried to obtain is put into the ceramic crucible of 10ml, is forged in the tube furnace being placed under nitrogen atmosphere
Burn, 600 DEG C are warming up to the speed of 15 DEG C/min, 2h is incubated at 600 DEG C, that is, obtain graphitiferous phase carbon nitride and sulphur regulation and control graphite
The nitridation carbon complex of phase carbon nitride.
Embodiment 5
Concentrated sulfuric acid dissolution graphite phase carbon nitride：Take 1g graphite phase carbon nitrides to be added in the round-bottomed flask of 25ml, then add
Enter the concentrated sulfuric acid of 10ml, oil bath is heated with stirring to 300 DEG C, heats 1h, treat that graphite phase carbon nitride all dissolves, be cooled to room temperature,
It is the concentrated sulfuric acid solution of the graphite phase carbon nitride of 100mg/ml to obtain the concentration of graphite phase carbon nitride.
Graphite phase carbon nitride is mixed：The concentrated sulfuric acid solution for taking 1ml graphite phase carbon nitrides adds the polysulfides of 1.4g tri- to it
Cyanic acid, so that sulphur regulation and control carbonitride and carbonitride ratio are 1 in the compound for finally giving:50, the mixture glass that will be obtained
Glass rod stirs into pasty state, is subsequently adding the secondary water of 30ml, uses magnetic stirrer 30min, stands 1h, reuses Bu Shi leakages
Bucket carries out suction filtration, then by sample drying.
Calcining：The sample that will be dried to obtain is put into the ceramic crucible of 10ml, is forged in the tube furnace being placed under nitrogen atmosphere
Burn, 600 DEG C are warming up to the speed of 5 DEG C/min, 2h is incubated at 600 DEG C, that is, obtain graphitiferous phase carbon nitride and sulphur regulation and control graphite
The compound of phase carbon nitride.
In embodiment 1-5, during graphite phase carbon nitride is reacted with trithiocyanuric acid, the addition situation such as table 1 of each reactant
It is shown.
Table 1
Embodiment 6
Graphite phase carbon nitride containing different proportion and sulphur that embodiment 1-3 is obtained regulate and control the compound of graphite phase carbon nitride
Photocatalyzed Hydrogen Production performance test is carried out, the whole hydrogen system that produces uses the xenon lamp of 300W as light source, and operating voltage is 15A, and
It is λ to control the light source for producing using optical filter>420nm, ensures to be reacted at room temperature at whole system, most by circulation
The gas for producing afterwards is detected by TCD detectors.It is as shown in Figure 1 that the hydrogen-producing speed for obtaining changes over time situation.Wherein Fig. 1's
Abscissa is the reaction time, and unit is hour, and ordinate is the mole for producing hydrogen, and unit is μm ol.
Find out as shown in Figure 1, compared to simple graphite phase carbon nitride, graphite phase carbon nitride and sulphur regulation and control graphite-phase are nitrogenized
The compound that carbon is constituted, effective Photocatalyzed Hydrogen Production performance is greatly improved.Wherein, the graphite-phase nitridation that embodiment 2 is obtained
Carbon is 1 with sulphur regulation and control graphite phase carbon nitride ratio:9 compound (i.e. CN-CNS-0.1) Photocatalyzed Hydrogen Production effect is best.This be by
In as shown in Fig. 2 in illumination, electrons are energized on conduction band and are left in valence band in graphite phase carbon nitride (CN) valence band
Hole, because the conduction band of sulphur regulation and control graphite phase carbon nitride (CNS) is lower than the conduction band of graphite phase carbon nitride, effect of the electronics in potential
Under move to sulphur regulate and control graphite phase carbon nitride conduction band；The valence band of the graphite phase carbon nitride of sulphur regulation and control simultaneously also compares graphite phase carbon nitride
Valence band it is low, hole will be moved in the valence band of graphite phase carbon nitride in the presence of potential.Therefore by therebetween
On a molecular scale compound, electronics has obtained separating well with hole.
Claims (9)
1. a kind of preparation method of graphite phase carbon nitride compound, it is characterised in that comprise the following steps：
(1) graphite phase carbon nitride is mixed with the concentrated sulfuric acid, heats and stir, graphite phase carbon nitride is dissolved completely in the concentrated sulfuric acid
In, obtain the concentrated sulfuric acid solution of graphite phase carbon nitride；
(2) trithiocyanuric acid is added in the concentrated sulfuric acid solution of graphite phase carbon nitride obtained in step (1), is added after being sufficiently mixed
Poor solvent, point isolated precipitation is simultaneously dried；
(3) sample that step (2) is dried to obtain is placed in inert atmosphere, 400-600 DEG C is calcined 1-3 hours, that is, obtain graphite
Phase carbon nitride compound, the graphite phase carbon nitride compound is made up of graphite phase carbon nitride with sulphur regulation and control graphite phase carbon nitride
Compound.
2. the preparation method of graphite phase carbon nitride compound according to claim 1, it is characterised in that in step (1), institute
Heating-up temperature is stated for 60~300 DEG C.
3. the preparation method of graphite phase carbon nitride compound according to claim 1, it is characterised in that in step (1), institute
State in the concentrated sulfuric acid solution of graphite phase carbon nitride, the concentration of graphite phase carbon nitride is 50mg/ml~200mg/ml.
4. the preparation method of graphite phase carbon nitride compound according to claim 1, it is characterised in that regulating step (2)
The addition of middle trithiocyanuric acid, in making the compound for finally giving, the graphite phase carbon nitride and graphite phase carbon nitride of sulphur regulation and control
Ratio be 1:99—1:4.
5. the preparation method of graphite phase carbon nitride compound according to claim 1, it is characterised in that in step (2), institute
State that to be sufficiently mixed be that the mixture of the concentrated sulfuric acid solution of graphite phase carbon nitride and trithiocyanuric acid is stirred into pasty state.
6. the preparation method of graphite phase carbon nitride compound according to claim 1, it is characterised in that in step (2), institute
Poor solvent is stated for secondary water.
7. the preparation method of graphite phase carbon nitride compound according to claim 1, it is characterised in that in step (3), institute
Inert atmosphere is stated for nitrogen atmosphere.
8. a kind of graphite phase carbon nitride compound, it is characterised in that the graphite phase carbon nitride compound is by claim 1~7
Preparation method described in middle any one is obtained.
9. a kind of photochemical catalyst, it is characterised in that the photochemical catalyst is that the graphite phase carbon nitride according to claim 8 is answered
Compound.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701583A (en) * | 2019-02-25 | 2019-05-03 | 武汉理工大学 | A kind of defect regulation high activity graphite phase carbon nitride and preparation method thereof |
| CN110560129A (en) * | 2019-09-10 | 2019-12-13 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of modified carbon nitride for improving tetracycline degradation efficiency, and product and application thereof |
| CN112023971A (en) * | 2020-08-26 | 2020-12-04 | 中国科学院山西煤炭化学研究所 | Application of cyano-modified carbon nitride in phenol photo-mineralization field |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127948A (en) * | 2013-02-26 | 2013-06-05 | 福州大学 | Polymer photocatalyst, and method of water-phase photo-catalytic selective alcohol oxidation |
| CN103861632A (en) * | 2014-04-07 | 2014-06-18 | 吉林大学 | Preparation method for multi-hole carbon nitride photocatalytic material doped with sulphur |
| CN105664997A (en) * | 2016-03-18 | 2016-06-15 | 中国海洋大学 | Method for preparing carbon nitride hetero-junction photocatalysts and application thereof |
-
2016
- 2016-12-05 CN CN201611103718.9A patent/CN106732720B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127948A (en) * | 2013-02-26 | 2013-06-05 | 福州大学 | Polymer photocatalyst, and method of water-phase photo-catalytic selective alcohol oxidation |
| CN103861632A (en) * | 2014-04-07 | 2014-06-18 | 吉林大学 | Preparation method for multi-hole carbon nitride photocatalytic material doped with sulphur |
| CN105664997A (en) * | 2016-03-18 | 2016-06-15 | 中国海洋大学 | Method for preparing carbon nitride hetero-junction photocatalysts and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| JINSHUI ZHANG等: "A Facile Band Alignment of Polymeric Carbon Nitride Semiconductors to Construct Isotype Heterojunctions", 《ANGEW. CHEM. INT. ED.》 * |
| ZHIXIN ZHOU等: "Dissolution and Liquid Crystals Phase of 2D Polymeric Carbon Nitride", 《J. AM. CHEM. SOC.》 * |
| 湛宗升等: "一种石墨相氮化碳复合物光催化剂及其制备方法", 《中国知网》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701583A (en) * | 2019-02-25 | 2019-05-03 | 武汉理工大学 | A kind of defect regulation high activity graphite phase carbon nitride and preparation method thereof |
| CN110560129A (en) * | 2019-09-10 | 2019-12-13 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of modified carbon nitride for improving tetracycline degradation efficiency, and product and application thereof |
| CN110560129B (en) * | 2019-09-10 | 2022-07-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of modified carbon nitride for improving tetracycline degradation efficiency, and product and application thereof |
| CN112023971A (en) * | 2020-08-26 | 2020-12-04 | 中国科学院山西煤炭化学研究所 | Application of cyano-modified carbon nitride in phenol photo-mineralization field |
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