CN106629984B - Molybdenum sulfide cooperates with azepine grapheme material and the application near infrared light denitrogenation - Google Patents
Molybdenum sulfide cooperates with azepine grapheme material and the application near infrared light denitrogenation Download PDFInfo
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- CN106629984B CN106629984B CN201611242725.7A CN201611242725A CN106629984B CN 106629984 B CN106629984 B CN 106629984B CN 201611242725 A CN201611242725 A CN 201611242725A CN 106629984 B CN106629984 B CN 106629984B
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- molybdenum sulfide
- azepine
- ammonia nitrogen
- grapheme material
- compound
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- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 title claims abstract description 72
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 48
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 230000015556 catabolic process Effects 0.000 claims abstract description 30
- 238000006731 degradation reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 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 9
- 230000003287 optical effect Effects 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 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
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910052961 molybdenite Inorganic materials 0.000 description 24
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- 238000002835 absorbance Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 229910004619 Na2MoO4 Inorganic materials 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
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 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
- 239000011941 photocatalyst Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000000926 separation method 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
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 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
- 238000001237 Raman spectrum Methods 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
- 230000008859 change Effects 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
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 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
- 238000012545 processing Methods 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
- 238000005987 sulfurization reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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 kind of molybdenum sulfide collaboration azepine grapheme material and the applications near infrared light denitrogenation.The composite material includes molybdenum sulfide and is distributed in the layer structure of the azepine graphene surface and/or the azepine graphene.The compound azepine grapheme material of molybdenum sulfide of the invention is as photochemical catalyst, the near infrared light in sunlight can be utilized by molybdenum sulfide, azepine graphene etc., one step of ammonia nitrogen is degraded to nitrogen to release, the utilization to solar energy is greatly improved, and after the photochemical catalyst is reused 5-10 times, the degradation rate of ammonia nitrogen is still > 87%.
Description
Technical field
The present invention relates to a kind of compound azepine grapheme material of molybdenum sulfide and its applications in photocatalytic degradation ammonia nitrogen.
Background technique
It can solve environmental energy problem using the sun, utilize TiO originating from Fujishima in 19722Optoelectronic pole electrolysis water
Hydrogen manufacturing, subsequent Carey were reported in 1976 and are utilized TiO2The toxicity of more chlorine diphenol is eliminated in photochemical catalytic oxidation, from this, using too
Sun can degrade environmental contaminants research rapidly become people research hot spot.But TiO2It can only be left using solar energy 4% is accounted for
Right ultraviolet light, to TiO2It is doped and develops Fe2O3、WO3、Bi2WO6Equal new catalysts, although part is solved to can
Light-exposed Utilizing question, but account for the infrared light of solar energy 46% it is still necessary to develop and use.
MoS2It is a kind of and graphene two-dimensional material with similar structure.As a kind of semiconductor light-catalyst, people
Have studied MoS2Hydrogen-producing characteristic under visible optical radiation.And in the application aspect of near infrared light, document only reports MoS2For
The research of photo-thermal drug release treating cancer.As a kind of semiconductor material, MoS2Forbidden bandwidth be 1.29eV, theoretical absorption
Sideband may extend to 961nm, and near infrared light can be absorbed, 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, theoretically
Sunlight can be utilized with hypersorption；In addition, NG has higher carrier transport rate, lower photoproduction compared with graphene
Electron/hole-recombination rate, higher quantum yield, therefore there is stronger photocatalytic activity.By NG and MoS2It is compound, it is expected to make
The standby NG-MoS for having catalytic activity near infrared light2Hydridization photochemical catalyst, makes full use of solar energy to realize.
Summary of the invention
The purpose of the present invention is to provide a kind of molybdenum sulfide collaboration azepine grapheme material and near infrared light denitrogenation
Using with overcome the deficiencies in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
It include molybdenum sulfide and azepine graphene the embodiment of the invention provides a kind of compound azepine grapheme material of molybdenum sulfide,
The molybdenum sulfide is distributed in the layer structure of the azepine graphene surface and/or the azepine graphene, wherein the sulphur
Changing molybdenum hasSpace group structure.
Further, the partial size 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%.
Preparation method the embodiment of the invention provides a kind of compound azepine grapheme material of molybdenum sulfide includes:
Molybdenum sulfide solid is provided；
Azepine graphene, molybdenum sulfide solid are uniformly mixed to obtained mixed liquor in solvent, later by mixed liquor in temperature
6-10h is reacted under the conditions of being 100-150 DEG C, the compound azepine grapheme material of molybdenum sulfide is made.
The embodiment of the invention also provides the compound azepine grapheme materials of the molybdenum sulfide in photocatalytic degradation ammonia nitrogen
Purposes.
The embodiment of the invention also provides a kind of methods of degradation of ammonia nitrogen comprising: 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-Na2CO3Buffer solution adjust the pH containing ammonia nitrogen solution
Value.
More preferred, the wavelength X range of the near infrared light is 780nm-2500nm.
More preferably, 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 include: by the aqueous solution containing ammonia nitrogen with
The compound azepine grapheme material of molybdenum sulfide, which is mixed into, to be protected from light in device, and is set at the illumination window for being protected from light device
Set the optical filter that only near infrared light can be made to pass through, later with light source irradiate described in be protected from light device, realize the de- of ammonia nitrogen in water body
It removes.
Compared with prior art, the invention has the advantages that
(1) composite photo-catalyst of the invention, azepine graphene including stratiform and is distributed in the azepine graphene table
The molybdenum sulfide in face after compound azepine graphene, accelerates the transfer of light induced electron, leads to absorption spectrum Einstein shift, increases pair
The utilization rate of solar energy, and after the catalyst repetition catalytic degradation ammonia nitrogen 5-10 times, the degradation rate of ammonia nitrogen is still > 90%.
(2) one step of ammonia nitrogen is degraded to nitrogen using near infrared light light by the preparation method of composite photo-catalyst of the invention
It releases, and without adding extra oxidant, thus reduce costs, and photochemical catalyst preparation process is simple, it is easy to operate.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
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 diagram；
Fig. 3 is MoS in the embodiment of the present invention 22, NG and NG-MoS2Raman spectrogram；
Fig. 4 a- Fig. 4 d is MoS in the embodiment of the present invention 12, NG and NG-MoS2TEM figure, wherein Fig. 4 a be azepine graphene
TEM figure, Fig. 4 b be molybdenum sulfide TEM scheme, Fig. 4 c and Fig. 4 d be the compound azepine grapheme material of molybdenum sulfide TEM scheme；
Fig. 5 is NG-MoS in the embodiment of the present invention 12The curve graph of ammonia nitrogen degradation rate after repeating 7.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, with reference to the accompanying drawing to specific reality of the invention
The mode of applying is described in detail.The example of these preferred embodiments is illustrated in the accompanying drawings.Shown in attached drawing and according to
The embodiments of the present invention of attached drawing description are only exemplary, and the present invention is not limited to these embodiments.
Here, it should also be noted that, in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only
Show with closely related structure and/or processing step according to the solution of the present invention, and be omitted little with relationship of the present invention
Other details.
Reaction mechanism of the invention the following steps are included:
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)
It is reaction mechanism figure of the invention referring to Fig. 1.
It include molybdenum sulfide and azepine graphene the embodiment of the invention provides a kind of compound azepine grapheme material of molybdenum sulfide,
The molybdenum sulfide is distributed in the layer structure of the azepine graphene surface and/or the azepine graphene, wherein the sulphur
Changing molybdenum hasSpace group structure.
Further, the partial size 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%.
Preparation method the embodiment of the invention provides a kind of compound azepine grapheme material of molybdenum sulfide includes:
Molybdenum sulfide solid is provided；
Azepine graphene, molybdenum sulfide solid are uniformly mixed to obtained mixed liquor in solvent, later by mixed liquor in temperature
6-10h is reacted under the conditions of being 100-150 DEG C, the compound azepine grapheme material of molybdenum sulfide is made.
The embodiment of the invention also provides the compound azepine grapheme materials of the molybdenum sulfide in photocatalytic degradation ammonia nitrogen
Purposes.
The embodiment of the invention also provides a kind of methods of degradation of ammonia nitrogen comprising: 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-Na2CO3Buffer solution adjust the pH containing ammonia nitrogen solution
Value.
More preferred, the wavelength X range of the near infrared light is 780nm-2500nm.
More preferably, 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 include: by the aqueous solution containing ammonia nitrogen with
The compound azepine grapheme material of molybdenum sulfide, which is mixed into, to be protected from light in device, and is set at the illumination window for being protected from light device
Set the optical filter that only near infrared light can be made to pass through, later with light source irradiate described in be protected from light device, realize the de- of ammonia nitrogen in water body
It removes.
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 is provided and is protected from light device, the optical filter can cover described be protected from light
Device top,
(2) pH value of the sample to be tested containing ammonia nitrogen is adjusted to mix after alkalinity with the compound azepine grapheme material of molybdenum sulfide
It is placed in being protected from light device and being covered with the optical filter in step (1), is placed in light source under stirring, uses nessler reagent later
Method is per the absorbance for measuring remaining ammonia nitrogen solution every other hour.
Further, the Na's reagent includes: the ammonia nitrogen solution taken in 1mL step (2), adds 1.5mL nessler reagent,
1mL potassium sodium tartrate solution is diluted to 50mL, measures the absorbance at 388nm with T1901 ultraviolet-uisible spectrophotometer, according to
The degradation rate of following formula calculating 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, after the compound azepine grapheme material of the molybdenum sulfide repeats catalytic degradation ammonia nitrogen 5-10 times, ammonia nitrogen
Degradation rate is still > 87%.
Technology of the 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 be 100mL beaker in, stirring until all dissolution, be then transferred in polytetrafluoroethylene (PTFE) inner sleeve, addition go from
Sub- water dissolves solid sufficiently and inner sleeve is placed in stainless steel outer sleeve cylinder to the 80% of total volume, seals, 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.Obtained black
Solid dry 6h, the MoS of system in 40 DEG C of baking ovens2Semiconductor material, b show the TEM figure of molybdenum sulfide, Ke Yiqing referring to fig. 4
Clear the layer structure for seeing molybdenum sulfide.
(2) preparation of azepine graphene (NG): accurately weighing graphene oxide (0.22g) and be dissolved in 100ml deionized water,
Ultrasound is to dispersion, the NH configured later3·H2O (1.0mol/L) adjust pH value be about 10 take again urea (22.0g, 99%) be added
2h is mixed in above-mentioned solution.It will be added in mixed liquor under hydrazine hydrate (2.5mL 0.16mol) magnetic agitation again, later above-mentioned
Mixed liquor is transferred to flask (three mouthfuls, 250mL), controls 80 DEG C of temperature, and magnetic agitation is condensed back reaction for 24 hours, is filtered, washing,
(70 DEG C, 6h) dryings of temperature are controlled in vacuum tank, and the azepine graphene is made, a is that the TEM of azepine graphene schemes referring to fig. 4,
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 hydro-thermal reaction 24 hours.Obtain difference
The NG-MoS of NG content2Nanometer, composite semiconductor material.The MoS for being 5% with NG content in photocatalysis experiment2As photochemical catalyst.
Shown in Figure 2, the diffraction maximum at 2 θ=14.2 °, 33.5 °, 39.5 ° and 59.0 ° corresponds respectively to MoS2(002),
(100), (103) and (110) crystal face indexes, MoS2With NG-MoS2Diffraction maximum and standard diagram (JCPDS37-1492) unanimously,
Thus may determine that gained sample is MoS2(space group is), c and Fig. 4 d is the compound azepine graphite of molybdenum sulfide referring to fig. 4
The TEM figure of alkene material is it can be seen that molybdenum sulfide is grown in the surface of azepine graphene, and MoS in hybrid catalyst2With preferable
Crystallinity.
(5) photocatalysis is tested: being encased the wall of cup of a 100ml beaker with masking foil, to avoid ultraviolet light and visible light
It into reaction system, is covered on beaker mouth with λ > 780nm cut-off type optical filter, to guarantee to only have near infrared radiation to enter light
300W ultraviolet-visible light lamp is placed in above reactor by reactor.Certain density ammonia nitrogen solution is added in beaker, uses
NaHCO3-Na2CO3(0.1mol/L) buffer solution adjusts pH value, and a certain amount of catalyst is added into beaker, is placed under light source,
Magnetic stirrer, per the absorbance for measuring remaining ammonia nitrogen solution every other hour.1ml ammonia nitrogen solution is taken, 1.5ml Na Shi is added to try
Agent, 1ml potassium sodium tartrate solution are diluted to 50ml, measure the absorbance at 388nm with T1901 ultraviolet-uisible spectrophotometer,
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) stability of hybrid catalyst catalyst stability: is evaluated by multiple circulation experiment.NG-MoS2Catalysis
The degradation rate of agent continuous 7 catalytic degradation ammonia nitrogens under near infrared radiation.Therapy lasted 8h each time, in degradation knot each time
Shu Hou is washed to obtain catalyst, is then further continued for that the catalyst is recycled by centrifuge separation, deionized water.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 be 100mL beaker in, stirring until all dissolution, be then transferred in polytetrafluoroethylene (PTFE) inner sleeve, addition go from
Sub- water dissolves solid sufficiently and inner sleeve is placed in stainless steel outer sleeve cylinder to the 80% of total volume, seals, 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.Obtained black
Solid dry 6h, the MoS of system in 40 DEG C of baking ovens2Semiconductor material.
(2) preparation of azepine graphene (NG): accurately weighing graphene oxide (0.22g) and be dissolved in 100ml deionized water,
Ultrasound is to dispersion, the NH configured later3·H2O (1.0mol/L) adjust pH value be about 10 take again urea (44.0g, 99%) be added
2h is mixed in above-mentioned solution.It will be added in mixed liquor under hydrazine hydrate (2.5mL 0.16mol) magnetic agitation again, later above-mentioned
Mixed liquor is transferred to flask (three mouthfuls, 250mL), controls 80 DEG C of temperature, and magnetic agitation is condensed back reaction for 24 hours, is filtered, washing,
(70 DEG C, 6h) dryings of temperature are controlled in vacuum tank, and the azepine graphene is made.
(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 hydro-thermal reaction 24 hours.Obtain difference
The NG-MoS of NG content2Nanometer, composite semiconductor material.The MoS for being 7% with NG content in photocatalysis experiment2As photochemical catalyst.
It is shown in Figure 3, MoS2Unit cell is belonged to according to made of hexagonal symmetry stackingSpace groupAccording to right
Title property, MoS2Vibration mode with 4 Raman actives:E1g,A1g [32], and it is located at 385cm-1And 408cm-1Place
Raman peaks are respectively belonging toAnd A1gVibration, this further demonstrates that prepared sample is MoS2, NG-MoS2Raman spectrum go out
The feature of molybdenum sulfide is showedAnd A1gVibration mode, while in 1600cm-1And 1335cm-1Place observes two small peaks, right respectively
It should be displaced in the G band and D band of graphene, this further demonstrates that NG and MoS2Success is compound.
(5) photocatalysis is tested: being encased the wall of cup of a 100ml beaker with masking foil, to avoid ultraviolet light and visible light
It into reaction system, is covered on beaker mouth with λ > 780nm cut-off type optical filter, to guarantee to only have near infrared radiation to enter light
300W ultraviolet-visible light lamp is placed in above reactor by reactor.Certain density ammonia nitrogen solution is added in beaker, uses
NaHCO3-Na2CO3(0.1mol/L) buffer solution adjusts pH value, and a certain amount of catalyst is added into beaker, is placed under light source,
Magnetic stirrer, per the absorbance for measuring remaining ammonia nitrogen solution every other hour.1ml ammonia nitrogen solution is taken, 1.5ml Na Shi is added to try
Agent, 1ml potassium sodium tartrate solution are diluted to 50ml, measure the absorbance at 388nm with T1901 ultraviolet-uisible spectrophotometer,
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) stability of hybrid catalyst catalyst stability: is evaluated by multiple circulation experiment.NG-MoS2Catalysis
The degradation rate of agent continuous 5 catalytic degradation ammonia nitrogens under near infrared radiation.Therapy lasted 8h each time, in degradation knot each time
Shu Hou is washed to obtain catalyst, is then further continued for that the catalyst is recycled by centrifuge separation, deionized water.It is recycled at 5 times
After degradation of ammonia nitrogen, ammonia nitrogen removal frank is still 90% or more.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of method of degradation of ammonia nitrogen, characterized by comprising: 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；
Wherein, the compound azepine grapheme material of the molybdenum sulfide includes molybdenum sulfide and azepine graphene, and the molybdenum sulfide is distributed in
In the layer structure of the azepine graphene surface and/or the azepine graphene, wherein the molybdenum sulfide hasIt is empty
Between group structure, the partial size of the compound azepine grapheme material of molybdenum sulfide is 4.0-5.2nm, and adjacent molybdenum sulfide interlamellar spacing is
0.55-0.65nm, the specific surface area of the compound azepine grapheme material of molybdenum sulfide are 8-9m2/ g, the azepine graphene in
Mass percent in the compound azepine grapheme material of molybdenum sulfide is 1-10wt%.
2. the method for degradation of ammonia nitrogen according to claim 1, which is characterized in that the compound azepine graphene of the molybdenum sulfide
The preparation method of material includes:
Molybdenum sulfide solid is provided；
Azepine graphene, molybdenum sulfide solid are uniformly mixed to obtained mixed liquor in solvent, are in temperature by mixed liquor later
6-10h is reacted under the conditions of 100-150 DEG C, and the compound azepine grapheme material of molybdenum sulfide is made.
3. the method for degradation of ammonia nitrogen according to claim 1, it is characterised in that: the range of the wavelength X of the near infrared light
For 780nm-2500nm.
4. the method for degradation of ammonia nitrogen according to claim 1, it is characterised in that: the compound azepine graphene material of molybdenum sulfide
The mass ratio of material and ammonia nitrogen is 100mg:5-50mg.
5. the method for degradation of ammonia nitrogen according to claim 1, it is characterised in that: by aqueous solution and molybdenum sulfide containing ammonia nitrogen
Compound azepine grapheme material, which is mixed into, to be protected from light in device, and is arranged at the illumination window for being protected from light device and only may be used
Make the optical filter that near infrared light passes through, later with light source irradiate described in be protected from light device, realize the removing of ammonia nitrogen in water body.
6. the method for degradation of ammonia nitrogen according to claim 5, it is characterised in that: use 0.1mol/L NaHCO3-Na2CO3
Buffer solution adjust the pH value of the aqueous solution containing ammonia nitrogen.
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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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| CN103111311A (en) * | 2013-02-20 | 2013-05-22 | 中国科学技术大学 | Composite nano material and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Hydrothermal synthesis of graphene hybrid with enhanced supercapacitor performancelayered molybdenum sulfide/N-doped;Bingqiao Xie et al.;《Carbon》;20160430;第99卷;第2.1-2.2节 |
| Molybdenum sulfide clusters-nitrogen-doped grapheme hybrid hydrogel film as an efficient three-dimensional hydrogen evolution electrocatalyst;Sheng Chen et al.;《Nano Energy》;20150131;第11卷;第12页第2栏第2-5段 |
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