CN106629984A - Molybdenum sulfide coordinated nitrogen-doped graphene material and application thereof in near-infrared light denitrification - Google Patents
Molybdenum sulfide coordinated nitrogen-doped graphene material and application thereof in near-infrared light denitrification Download PDFInfo
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- CN106629984A CN106629984A CN201611242725.7A CN201611242725A CN106629984A CN 106629984 A CN106629984 A CN 106629984A CN 201611242725 A CN201611242725 A CN 201611242725A CN 106629984 A CN106629984 A CN 106629984A
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- molybdenum sulfide
- azepine
- ammonia nitrogen
- grapheme material
- nitrogen
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 39
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 66
- 230000015556 catabolic process Effects 0.000 claims abstract description 27
- 238000006731 degradation reaction Methods 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 68
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 229910052961 molybdenite Inorganic materials 0.000 description 24
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 24
- 238000002835 absorbance Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011684 sodium molybdate Substances 0.000 description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NXMWOOVRJPJOSH-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.[Cl] Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.[Cl] NXMWOOVRJPJOSH-UHFFFAOYSA-N 0.000 description 1
- 241001125671 Eretmochelys imbricata Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The invention discloses a molybdenum sulfide coordinated nitrogen-doped graphene material and an application thereof in near-infrared light denitrification. The composite material comprises molybdenum sulfide and nitrogen-doped graphene, wherein the molybdenum sulfide is distributed on the surface of the nitrogen-doped graphene and/or in a layered structure of the nitrogen-doped graphene. The molybdenum sulfide compounded nitrogen-doped graphene material provided by the invention is used as a photocatalyst, and the near-infrared light in sunlight can be utilized through the molybdenum sulfide, the nitrogen-doped graphene and the like, so ammonia nitrogen can be further degraded into nitrogen gas and discharged, and the utilization of solar power is greatly improved; meanwhile, after the photocatalyst is repeatedly used for 5 to 10 times, the degradation rate of the ammonia nitrogen is still larger than 87%.
Description
Technical field
The present invention relates to a kind of compound azepine grapheme material of molybdenum sulfide and its application in photocatalytic degradation ammonia nitrogen.
Background technology
Environmental energy is solved the problems, such as using solar energy, is originated from Fujishima in 1972 and is utilized TiO2Optoelectronic pole electrolysis water
Hydrogen manufacturing, subsequent Carey was reported in 1976 and is utilized TiO2Photochemical catalytic oxidation eliminates the toxicity of many chlorine diphenol, from this, using too
The research of the positive environmental contaminants that can degrade rapidly becomes the focus of people's research.But, TiO2Can only be left using solar energy 4% is accounted for
Right ultraviolet light, to TiO2It is doped and develops Fe2O3、WO3、Bi2WO6Deng new catalyst, although partly solving pair can
See the Utilizing question of light, the exploitation but infrared light for accounting for solar energy 46% is still needed.
MoS2It is a kind of two-dimensional material with Graphene with similar structures.As a kind of semiconductor light-catalyst, people
Have studied MoS2Hydrogen-producing characteristic under visible radiation.And in the application aspect of near infrared light, document only reports MoS2For
The research of photo-thermal insoluble drug release treating cancer.As a kind of semi-conducting material, MoS2Energy gap be 1.29eV, theoretical absorption
Sideband may extend to 961nm, can absorb near infrared light, and this has laid scientific basic near infrared light photocatalysis.
On the other hand, azepine Graphene (N-doped graphene, NG) is a kind of zero gap semiconductor material, in theory
Sunshine can be utilized with hypersorption；Additionally, compared with Graphene, NG has higher carrier transport speed, lower photoproduction
Electron/hole-recombination rate, higher quantum yield, therefore with higher photocatalytic activity.By NG and MoS2It is compound, it is expected to system
For the NG-MoS for having catalysis activity near infrared light2Hydridization photochemical catalyst, to realizing making full use of solar energy.
The content of the invention
It is an object of the invention to provide a kind of molybdenum sulfide cooperates with azepine grapheme material and near infrared light denitrogenation
Using to overcome the deficiencies in the prior art.
To realize aforementioned invention purpose, the technical solution used in the present invention includes：
Embodiments providing a kind of compound azepine grapheme material of molybdenum sulfide includes molybdenum sulfide and azepine Graphene,
The molybdenum sulfide is distributed in the layer structure of the azepine graphenic surface and/or the azepine Graphene, wherein the sulphur
Change molybdenum to haveSpace group structure.
Further, the particle diameter of the compound azepine grapheme material of the molybdenum sulfide is 4.0-5.2nm.
Further, adjacent molybdenum sulfide interlamellar spacing is 0.55-0.65nm.
Further, the specific surface area of the compound azepine grapheme material of the molybdenum sulfide is 8-9m2/g。
Further, mass percent of the azepine Graphene in the compound azepine grapheme material of the molybdenum sulfide is
1-10wt%.
Embodiments providing a kind of preparation method of the compound azepine grapheme material of molybdenum sulfide includes：
Molybdenum sulfide solid is provided；
Azepine Graphene, molybdenum sulfide solid are well mixed into prepared mixed liquor in solvent, afterwards by mixed liquor in temperature
To react 6-10h under the conditions of 100-150 DEG C, the compound azepine grapheme material of described molybdenum sulfide is obtained.
The embodiment of the present invention additionally provides the compound azepine grapheme material of the molybdenum sulfide in photocatalytic degradation ammonia nitrogen
Purposes.
The embodiment of the present invention additionally provides a kind of method of degradation of ammonia nitrogen, and it includes：Under near infrared light illumination condition, with
The compound azepine grapheme material of molybdenum sulfide Direct Catalytic Oxidation ammonia nitrogen in alkaline atmosphere as photochemical catalyst, realizes ammonia in water body
The removing of nitrogen.
It is more preferred, using 0.1mol/L NaHCO3-Na2CO3Cushioning liquid adjust the pH containing ammonia nitrogen solution
Value.
More preferred, the wavelength X scope of the near infrared light is 780nm-2500nm.
More preferred, the mass ratio of the compound azepine grapheme material of the molybdenum sulfide and ammonia nitrogen is 100mg:5-50mg.
In one more preferred embodiment, a kind of method of degradation of ammonia nitrogen includes：By the aqueous solution containing ammonia nitrogen with
The compound azepine grapheme material mixing of molybdenum sulfide is inserted in lucifuge reactor, and is set at the illumination window of the lucifuge reactor
The optical filter that near infrared light can only passed through is put, afterwards the lucifuge reactor is irradiated with light source, realize the de- of ammonia nitrogen in water body
Remove.
Compared with prior art, advantages of the present invention includes：
(1) composite photo-catalyst of the invention, including the azepine Graphene of stratiform and it is distributed in the azepine Graphene table
The molybdenum sulfide in face, after being combined azepine Graphene, accelerates the transfer of light induced electron, causes absorption spectrum Einstein shift, and it is right to increase
The utilization rate of solar energy, and the catalyst repeats after catalytic degradation ammonia nitrogen 5-10 time, the degradation rate of ammonia nitrogen is still>90%.
(2) preparation method of composite photo-catalyst of the invention, nitrogen is degraded to using near infrared light light by the step of ammonia nitrogen one
Release, and unnecessary oxidant need not be added, so as to reduce cost, and photochemical catalyst preparation process is simple, easy to operate.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments described in invention, for those of ordinary skill in the art, on the premise of not paying creative work,
Can be with according to these other accompanying drawings of accompanying drawings acquisition.
Fig. 1 is the reaction mechanism figure of the embodiment of the present invention 1；
Fig. 2 is molybdenum sulfide (MoS in the embodiment of the present invention 12), azepine Graphene (NG) and azepine Graphene composite sulfuration molybdenum
(NG-MoS2) XRD；
Fig. 3 is MoS in the embodiment of the present invention 22, NG and NG-MoS2Raman spectrogram；
Fig. 4 a- Fig. 4 d are MoS in the embodiment of the present invention 12, NG and NG-MoS2TEM figure, wherein Fig. 4 a be azepine Graphene
TEM figures, Fig. 4 b scheme for the TEM of molybdenum sulfide, and Fig. 4 c and Fig. 4 d is the TEM figures of the compound azepine grapheme material of molybdenum sulfide；
Fig. 5 is NG-MoS in the embodiment of the present invention 12Repeat the curve map of ammonia nitrogen degradation rate after 7.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the accompanying drawings to the concrete reality of the present invention
The mode of applying is described in detail.The example of these preferred embodiments is illustrated in the accompanying drawings.Shown in accompanying drawing and according to
What the embodiments of the present invention of Description of Drawings were merely exemplary, and the present invention is not limited to these embodiments.
Here, also, it should be noted that in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only
The structure and/or process step closely related with scheme of the invention is shown, and is eliminated little with relation of the present invention
Other details.
The reaction mechanism of the present invention is comprised the following steps：
NH3+·OH→NH2+H2O........................(1)
NH2+·OH→NH+H2O.........................(2)
NH+·OH→N+H2O............................(3)
NHx+NHy→N2Hx+y(x, y=0,1,2) ... ... .. (4)
N2Hx+y+(x+y)OH→N2+(x+y)H2O..........(5)
Referring to the reaction mechanism figure that Fig. 1 is the present invention.
Embodiments providing a kind of compound azepine grapheme material of molybdenum sulfide includes molybdenum sulfide and azepine Graphene,
The molybdenum sulfide is distributed in the layer structure of the azepine graphenic surface and/or the azepine Graphene, wherein the sulphur
Change molybdenum to haveSpace group structure.
Further, the particle diameter of the compound azepine grapheme material of the molybdenum sulfide is 4.0-5.2nm.
Further, adjacent molybdenum sulfide interlamellar spacing is 0.55-0.65nm.
Further, the specific surface area of the compound azepine grapheme material of the molybdenum sulfide is 8-9m2/g。
Further, mass percent of the azepine Graphene in the compound azepine grapheme material of the molybdenum sulfide is
1-10wt%.
Embodiments providing a kind of preparation method of the compound azepine grapheme material of molybdenum sulfide includes：
Molybdenum sulfide solid is provided；
Azepine Graphene, molybdenum sulfide solid are well mixed into prepared mixed liquor in solvent, afterwards by mixed liquor in temperature
To react 6-10h under the conditions of 100-150 DEG C, the compound azepine grapheme material of described molybdenum sulfide is obtained.
The embodiment of the present invention additionally provides the compound azepine grapheme material of the molybdenum sulfide in photocatalytic degradation ammonia nitrogen
Purposes.
The embodiment of the present invention additionally provides a kind of method of degradation of ammonia nitrogen, and it includes：Under near infrared light illumination condition, with
The compound azepine grapheme material of molybdenum sulfide Direct Catalytic Oxidation ammonia nitrogen in alkaline atmosphere as photochemical catalyst, realizes ammonia in water body
The removing of nitrogen.
It is more preferred, using 0.1mol/L NaHCO3-Na2CO3Cushioning liquid adjust the pH containing ammonia nitrogen solution
Value.
More preferred, the wavelength X scope of the near infrared light is 780nm-2500nm.
More preferred, the mass ratio of the compound azepine grapheme material of the molybdenum sulfide and ammonia nitrogen is 100mg:5-50mg.
In one more preferred embodiment, a kind of method of degradation of ammonia nitrogen includes：By the aqueous solution containing ammonia nitrogen with
The compound azepine grapheme material mixing of molybdenum sulfide is inserted in lucifuge reactor, and is set at the illumination window of the lucifuge reactor
The optical filter that near infrared light can only passed through is put, afterwards the lucifuge reactor is irradiated with light source, realize the de- of ammonia nitrogen in water body
Remove.
In one more preferred embodiment, a kind of processing method of degradation of ammonia nitrogen is specifically included：
(1) near infrared light cut-off type optical filter and lucifuge reactor are provided, the optical filter can cover the lucifuge reaction
Device top,
(2) pH value of the testing sample containing ammonia nitrogen is adjusted to mix with the compound azepine grapheme material of molybdenum sulfide after alkalescence
The lucifuge reactor that is placed in step (1) is simultaneously covered with the optical filter, is placed under stirring in light source, afterwards using nessler reagent
Method is per the absorbance for determining remaining ammonia nitrogen solution every other hour.
Further, the Na's reagent includes：The ammonia nitrogen solution in 1mL steps (2), plus 1.5mL nessler reagents are taken,
1mL potassium sodium tartrate solutions are diluted to 50mL, and with T1901 ultraviolet-uisible spectrophotometers the absorbance at 388nm is determined, according to
Below equation calculates the degradation rate of ammonia nitrogen：
Ammonia nitrogen degradation rate=(1-Ci/C0) × 100%=(1-Ai/A0) × 100%
In formula, C0For the initial concentration of ammonia nitrogen, A0For the absorbance of initial soln, CiFor the concentration of remaining ammonia nitrogen, AiIt is surplus
The absorbance of remaining ammonia nitrogen.
Further, the compound azepine grapheme material of the molybdenum sulfide repeats after catalytic degradation ammonia nitrogen 5-10 time, ammonia nitrogen
Degradation rate is still>87%.
The technology of the present invention is further explained below in conjunction with drawings and Examples.
Embodiment 1
(1)MoS2Preparation：Take 1.21g Na2MoO4·2H2O (0.005mol), 1.56g CS (NH2)2(0.020mol),
In volume in the beaker of 100mL, stirring until all dissolvings, in then proceeding to polytetrafluoroethylene (PTFE) inner sleeve, addition go from
Sub- water makes solid fully dissolve and inner sleeve is placed in stainless steel outer sleeve cylinder to the 80% of cumulative volume, sealing, is heated to 200 DEG C,
Reaction 24 hours.Then sample is cooled down at room temperature, is washed with deionized, solable matter is removed.The black for obtaining
Solid is dried 6h, the MoS of system in 40 DEG C of baking ovens2Semi-conducting material, referring to Fig. 4 b the TEM figures of molybdenum sulfide, Ke Yiqing are shown
The clear layer structure that must see molybdenum sulfide.
(2) preparation of azepine Graphene (NG)：Accurately weigh graphene oxide (0.22g) and be dissolved in 100ml deionized waters,
Ultrasound is extremely disperseed, the NH for configuring afterwards3·H2O (1.0mol/L) regulations pH value is about 10 and takes urea (22.0g, 99%) addition again
Above-mentioned solution mixes 2h.To add in mixed liquor, afterwards above-mentioned under hydrazine hydrate (2.5mL 0.16mol) magnetic agitation again
Mixed liquor proceeds to flask (three mouthfuls, 250mL), controls 80 DEG C of temperature, and magnetic agitation, condensing reflux reaction 24h is filtered, washing,
(70 DEG C, 6h) dryings of temperature are controlled in vacuum tank, the azepine Graphene are obtained, schemed for the TEM of azepine Graphene referring to Fig. 4 a,
Prepared azepine Graphene is also lamellar structure.
(4)NG-MoS2Preparation.In synthesis MoS2During, Na2MoO4·2H2O and CS (NH2)2Mixed solution in
Face is separately added into the NG that mass fraction is respectively 1%, 3%, 5%, 7%, 9%, 200 DEG C of hydro-thermal reactions 24 hours.Obtain difference
The NG-MoS of NG contents2Nanometer, composite semiconductor material.With MoS that NG contents are 5% in photocatalysis experiment2As photochemical catalyst.
Shown in Figure 2, in 2 θ=14.2 °, the diffraction maximum at 33.5 °, 39.5 ° and 59.0 ° corresponds respectively to MoS2(002),
(100), (103) and (110) crystal face indexes, MoS2With NG-MoS2Diffraction maximum it is consistent with standard diagram (JCPDS37-1492),
Thus may determine that gained sample is MoS2(space group is), it is the compound azepine graphite of molybdenum sulfide referring to Fig. 4 c and Fig. 4 d
The TEM figures of alkene material are it can be seen that molybdenum sulfide is grown in the surface of azepine Graphene, and MoS in hybrid catalyst2With preferable
Crystallinity.
(5) photocatalysis experiment：The wall of cup of one 100ml beaker is encased with masking foil, to avoid ultraviolet light and visible ray
Into reaction system, λ is used>780nm cut-off type optical filters are covered on beaker mouth, to ensure to only have near infrared radiation to enter light
Reactor, by 300W ultraviolet-visible light lamps reactor top is placed in.Certain density ammonia nitrogen solution is added in beaker, is used
NaHCO3-Na2CO3(0.1mol/L) cushioning liquid adjusts pH value, and a certain amount of catalyst is added in beaker, under being placed in light source,
Magnetic stirrer, per the absorbance for determining remaining ammonia nitrogen solution every other hour.Take 1ml ammonia nitrogen solutions, plus 1.5ml Na Shi examinations
Agent, 1ml potassium sodium tartrate solutions are diluted to 50ml, and with T1901 ultraviolet-uisible spectrophotometers the absorbance at 388nm is determined,
The degradation rate of ammonia nitrogen is calculated with this.
Ammonia nitrogen degradation rate=(1-Ci/C0) × 100%=(1-Ai/A0) × 100%
In formula, C0For the initial concentration of ammonia nitrogen, A0For the absorbance of initial soln, CiFor the concentration of remaining ammonia nitrogen, AiIt is surplus
The absorbance of remaining ammonia nitrogen.
(6) catalyst stability：The stability of hybrid catalyst is evaluated by multiple circulation experiment.NG-MoS2Catalysis
The degradation rate of agent continuous 7 catalytic degradation ammonia nitrogens under near infrared radiation.Each time Therapy lasted 8h, ties in degraded each time
Shu Hou, by centrifugation, deionized water washing catalyst is obtained, and is then further continued for recycling the catalyst.Referring to Fig. 5,
After the compound azepine grapheme material of molybdenum sulfide is as photochemical catalyst photocatalytic degradation ammonia nitrogen 7 times ammonia nitrogen removal frank still 87% with
On.
Embodiment 2
(1)MoS2Preparation：Take 1.21g Na2MoO4·2H2O (0.005mol), 1.56g CS (NH2)2(0.020mol),
In volume in the beaker of 100mL, stirring until all dissolvings, in then proceeding to polytetrafluoroethylene (PTFE) inner sleeve, addition go from
Sub- water makes solid fully dissolve and inner sleeve is placed in stainless steel outer sleeve cylinder to the 80% of cumulative volume, sealing, is heated to 200 DEG C,
Reaction 24 hours.Then sample is cooled down at room temperature, is washed with deionized, solable matter is removed.The black for obtaining
Solid is dried 6h, the MoS of system in 40 DEG C of baking ovens2Semi-conducting material.
(2) preparation of azepine Graphene (NG)：Accurately weigh graphene oxide (0.22g) and be dissolved in 100ml deionized waters,
Ultrasound is extremely disperseed, the NH for configuring afterwards3·H2O (1.0mol/L) regulations pH value is about 10 and takes urea (44.0g, 99%) addition again
Above-mentioned solution mixes 2h.To add in mixed liquor, afterwards above-mentioned under hydrazine hydrate (2.5mL 0.16mol) magnetic agitation again
Mixed liquor proceeds to flask (three mouthfuls, 250mL), controls 80 DEG C of temperature, and magnetic agitation, condensing reflux reaction 24h is filtered, washing,
(70 DEG C, 6h) dryings of temperature are controlled in vacuum tank, the azepine Graphene is obtained.
(4)NG-MoS2Preparation.In synthesis MoS2During, Na2MoO4·2H2O and CS (NH2)2Mixed solution in
Face is separately added into the NG that mass fraction is respectively 1%, 3%, 5%, 7%, 9%, 200 DEG C of hydro-thermal reactions 24 hours.Obtain difference
The NG-MoS of NG contents2Nanometer, composite semiconductor material.With MoS that NG contents are 7% in photocatalysis experiment2As photochemical catalyst.
It is shown in Figure 3, MoS2Unit cell is formed according to hexagonal symmetry stacking, is belonged toSpace groupAccording to right
Title property, MoS2Vibration mode with 4 Raman actives:E1g,A1g [32], and positioned at 385cm-1And 408cm-1Place
Raman peaks are respectively belonging toAnd A1gVibration, this further demonstrates that prepared sample is MoS2, NG-MoS2Raman spectrogram go out
The feature of molybdenum sulfide is showedAnd A1gVibration mode, while in 1600cm-1And 1335cm-1Place observes two small peaks, right respectively
Should be in the G of Graphene bands and D band displacements, this further demonstrates that NG and MoS2It is successfully compound.
(5) photocatalysis experiment：The wall of cup of one 100ml beaker is encased with masking foil, to avoid ultraviolet light and visible ray
Into reaction system, λ is used>780nm cut-off type optical filters are covered on beaker mouth, to ensure to only have near infrared radiation to enter light
Reactor, by 300W ultraviolet-visible light lamps reactor top is placed in.Certain density ammonia nitrogen solution is added in beaker, is used
NaHCO3-Na2CO3(0.1mol/L) cushioning liquid adjusts pH value, and a certain amount of catalyst is added in beaker, under being placed in light source,
Magnetic stirrer, per the absorbance for determining remaining ammonia nitrogen solution every other hour.Take 1ml ammonia nitrogen solutions, plus 1.5ml Na Shi examinations
Agent, 1ml potassium sodium tartrate solutions are diluted to 50ml, and with T1901 ultraviolet-uisible spectrophotometers the absorbance at 388nm is determined,
The degradation rate of ammonia nitrogen is calculated with this.
Ammonia nitrogen degradation rate=(1-Ci/C0) × 100%=(1-Ai/A0) × 100%
In formula, C0For the initial concentration of ammonia nitrogen, A0For the absorbance of initial soln, CiFor the concentration of remaining ammonia nitrogen, AiIt is surplus
The absorbance of remaining ammonia nitrogen.
(6) catalyst stability：The stability of hybrid catalyst is evaluated by multiple circulation experiment.NG-MoS2Catalysis
The degradation rate of agent continuous 5 catalytic degradation ammonia nitrogens under near infrared radiation.Each time Therapy lasted 8h, ties in degraded each time
Shu Hou, by centrifugation, deionized water washing catalyst is obtained, and is then further continued for recycling the catalyst.In 5 circulations
After degradation of ammonia nitrogen, ammonia nitrogen removal frank is still more than 90%.
It should be appreciated that above-described embodiment technology design only to illustrate the invention and feature, its object is to allow and are familiar with this
The personage of item technology will appreciate that present disclosure and implement according to this, can not be limited the scope of the invention with this.It is all
The equivalence changes made according to spirit of the invention or modification, all should be included within the scope of the present invention.
Claims (10)
1. a kind of molybdenum sulfide is combined azepine grapheme material, it is characterised in that including molybdenum sulfide and azepine Graphene, the sulfuration
Molybdenum is distributed in the layer structure of the azepine graphenic surface and/or the azepine Graphene, wherein the molybdenum sulfide has
P3 6/ mmc spaces group structure.
2. molybdenum sulfide according to claim 1 is combined azepine grapheme material, it is characterised in that：The molybdenum sulfide composite nitrogen
The particle diameter of miscellaneous grapheme material is 4.0-5.2nm, and adjacent molybdenum sulfide interlamellar spacing is 0.55-0.65nm；
And/or, the specific surface area of the compound azepine grapheme material of the molybdenum sulfide is 8-9m2/g。
3. molybdenum sulfide according to claim 1 is combined azepine grapheme material, it is characterised in that：The azepine Graphene in
Mass percent in the compound azepine grapheme material of the molybdenum sulfide is 1-10wt%.
4. molybdenum sulfide according to claim 1 is combined the preparation method of azepine grapheme material, it is characterised in that：
Molybdenum sulfide solid is provided；
Azepine Graphene, molybdenum sulfide solid are well mixed into prepared mixed liquor in solvent, are in temperature by mixed liquor afterwards
6-10h is reacted under the conditions of 100-150 DEG C, the compound azepine grapheme material of described molybdenum sulfide is obtained.
5. based on the compound azepine grapheme material of molybdenum sulfide any one of claim 1-3 in photocatalytic degradation ammonia nitrogen
Purposes.
6. a kind of method of degradation of ammonia nitrogen, it is characterised in that include：Under near infrared light illumination condition, with the compound azepine of molybdenum sulfide
Grapheme material Direct Catalytic Oxidation ammonia nitrogen in alkaline atmosphere as photochemical catalyst, realizes the removing of ammonia nitrogen in water body.
7. the method for degradation of ammonia nitrogen according to claim 6, it is characterised in that：Using 0.1mol/L NaHCO3-Na2CO3
Cushioning liquid adjust the pH value containing ammonia nitrogen solution.
8. the method for degradation of ammonia nitrogen according to claim 6, it is characterised in that：The scope of the wavelength X of the near infrared light
For 780nm-2500nm.
9. the method for degradation of ammonia nitrogen according to claim 6, it is characterised in that：The compound azepine Graphene material of the molybdenum sulfide
Material is 100mg with the mass ratio of ammonia nitrogen:5-50mg.
10. the method for degradation of ammonia nitrogen according to claim 6, it is characterised in that：By the aqueous solution containing ammonia nitrogen and sulfuration
The compound azepine grapheme material mixing of molybdenum is inserted in lucifuge reactor, and is arranged only at the illumination window of the lucifuge reactor
The optical filter that pass through can near infrared light, irradiates the lucifuge reactor with light source afterwards, realizes the removing of ammonia nitrogen in water body.
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|---|---|---|---|---|
| CN102698774A (en) * | 2012-06-08 | 2012-10-03 | 浙江大学 | Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material |
| CN103111311A (en) * | 2013-02-20 | 2013-05-22 | 中国科学技术大学 | Composite nano material and preparation method thereof |
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| CN102698774A (en) * | 2012-06-08 | 2012-10-03 | 浙江大学 | Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material |
| CN103111311A (en) * | 2013-02-20 | 2013-05-22 | 中国科学技术大学 | Composite nano material and preparation method thereof |
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Effective date of registration: 20191210 Address after: 215000 b4109 in No.1 Ruoshui Road, Suzhou Industrial Park, Suzhou City, Jiangsu Province Patentee after: Suzhou Nipu Environmental Technology Co., Ltd Address before: Keruilu high tech Zone of Suzhou City, Jiangsu Province, No. 1 215009 Patentee before: Suzhou University of Science and Technology |