CN106362783B - Graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst photocatalysis denitrogenation purposes - Google Patents
Graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst photocatalysis denitrogenation purposes Download PDFInfo
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- CN106362783B CN106362783B CN201610633033.9A CN201610633033A CN106362783B CN 106362783 B CN106362783 B CN 106362783B CN 201610633033 A CN201610633033 A CN 201610633033A CN 106362783 B CN106362783 B CN 106362783B
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- graphene
- zinc ferrite
- azepine
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- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 15
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 4
- 239000011029 spinel Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 10
- -1 Oxonium ion Chemical class 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000192700 Cyanobacteria Species 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- YFDLHELOZYVNJE-UHFFFAOYSA-L mercury diiodide Chemical compound I[Hg]I YFDLHELOZYVNJE-UHFFFAOYSA-L 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
- 239000005416 organic matter Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst photocatalysis denitrogenation purposes.Zinc ferrite intelligence photochemical catalyst optionally adsorbs and photocatalysis denitrogenation under visible light illumination for the graphene/azepine graphene-.The graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst includes graphene or azepine graphene and zinc ferrite, the zinc ferrite is distributed in the layer structure surface and/or inside of the graphene or azepine graphene, wherein the zinc ferrite is spinel structure, and the zinc ferrite has the space Fd3m group structure.Graphene provided by the invention/azepine graphene-zinc ferrite intelligence photochemical catalyst optionally photocatalysis denitrogenation, and sewage water denitrification can be realized under visible light illumination, after intelligence photochemical catalyst provided by the invention repeats photocatalysis denitrogenation 5-10 times, the denitrification percent of ammonia nitrogen is still 95% or more.Simple intelligent photochemical catalyst preparation method, low in raw material price, the condition provided by the invention stated is easily-controllable, substantially increases production efficiency.
Description
Technical field
The present invention relates to a kind of intelligent photochemical catalyst, in particular to a kind of graphenes/azepine graphene-zinc ferrite intelligence light
Catalyst and its selectively photocatalysis denitrogenation belong to photocatalysis technology field.
Background technique
Taihu Lake cyanobacteria contamination accident in 2007 causes highest attention of the whole nation to ammonia and nitrogen pollution, and ammonia nitrogen processing method is divided into life
Object method, physical method and chemical method.Currently, the ammonia nitrogen (< 100mg/L) of low concentration can pass through nitrification-denitrification technique denitrogenation, nitre
Change effect is divided into ammoxidation and nitrite-oxidizing, and the nitrate of formation by denitrification becomes gas and be discharged to reach denitrification effect.
But under the conditions of high ammonia nitrogen heavily contaminated, since bacterium is very sensitive to factors such as weather, temperature, organic matter, dissolved oxygens, the party
Method is at high cost, and the investment of management service is high, it is therefore desirable to develop new denitrification process.
With the development of science and technology, researcher, which explores, utilizes semiconductor material (predominantly TiO2) it is used as photochemical catalyst
Carry out degradation of ammonia nitrogen, but these research work are that exploitation solar energy purification environment has made positive trial, but photocatalytic degradation
Ammonia nitrogen lacks selectivity, and TiO2Its visible light can only cannot be utilized using the ultraviolet light in solar energy, therefore solar energy
Utilization rate is not high.
Therefore, it is necessary to develop the photochemical catalyst of efficient high selection, so as to it is quick, stable, lasting, cheap, cleanly realize
The target of denitrogenation.
Summary of the invention
The purpose of the present invention is to provide a kind of photocatalysis of graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst
Denitrogenation purposes, to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst selectively suction is provided in the embodiment of the present invention
Attached and photocatalysis denitrogenation purposes.The graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst include graphene and/or
Azepine graphene and zinc ferrite, the zinc ferrite be distributed in the graphene and/or azepine graphene layer structure surface and/
Or it is internal, wherein the zinc ferrite is spinel structure, and the zinc ferrite has the space Fd3m group structure.
A kind of preparation of graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst is additionally provided in the embodiment of the present invention
Method comprising following steps: soluble zinc salt, soluble ferric iron salt and graphene/azepine graphene are dissolved in solvent and mixed
Close uniformly, adjusting solution later is alkalinity, then solution is reacted 6-10h under the conditions of 150-200 DEG C, be made the graphene/
Azepine graphene-zinc ferrite intelligence photochemical catalyst.
Compared with prior art, the invention has the advantages that
(1) graphene provided by the invention/azepine graphene-zinc ferrite intelligence photochemical catalyst is optionally degraded water body
In ammonia nitrogen, and visible light denitrification can be effectively utilized.After the catalyst repeats photocatalysis denitrogenation 5-10 times, ammonia nitrogen takes off
Nitrogen rate is still 95% or more.
It (2) include graphene/azepine in graphene provided by the invention/azepine graphene-zinc ferrite intelligence photochemical catalyst
Graphene enhances the absorption rate of visible light, reduces the recombination rate of light induced electron and photohole, and intelligence of the invention
Energy photochemical catalyst can identify ammonia nitrogen, and its photocatalytic-oxidation chemical conversion nitrogen is released, and realize the cheap denitrogenation of water body.
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 zinc ferrite (ZnFe in the embodiment of the present invention 12O4), graphene-zinc ferrite (rG-ZnFe2O4), azepine graphite
Alkene-zinc ferrite (NG-ZnFe2O4) with the XRD diagram of graphene (rG)；
Fig. 2 is zinc ferrite (ZnFe in the embodiment of the present invention 12O4), graphene-zinc ferrite (rG-ZnFe2O4), absorption ammonia nitrogen
Graphene-zinc ferrite, adsorb graphene-zinc ferrite Raman spectrogram of ammonia nitrogen and rhodamine B simultaneously；
Fig. 3 a- Fig. 3 d is the TEM figure of different material in the embodiment of the present invention 1, and wherein Fig. 3 a is the TEM of graphene (rG)
Figure, Fig. 3 b is zinc ferrite (ZnFe2O4) TEM figure, Fig. 3 c be graphene-zinc ferrite (rG-ZnFe2O4) TEM figure, Fig. 3 d is
Azepine graphene-zinc ferrite (NG-ZnFe2O4) TEM figure；
Fig. 4 is graphene-zinc ferrite (rG-ZnFe in the embodiment of the present invention 12O4) reuse 8 times nitric efficiency with
The graph of relation of denitrogenation time；
Fig. 5 is graphene-zinc ferrite (rG-ZnFe in the embodiment of the present invention 12O4) catalyst degradation ammonia nitrogen photocatalysis drop
Solution curve figure；
Fig. 6 is graphene-zinc ferrite (rG-ZnFe in comparative example 1 of the present invention2O4) catalyst degradation ammonia nitrogen and rhodamine B
Photocatalytic degradation curve graph.
Fig. 7 is graphene-zinc ferrite (rG-ZnFe in comparative example 2 of the present invention2O4) catalyst degradation ammonia nitrogen and methyl orange
Photocatalytic degradation curve graph.
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)
A kind of graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst selectively suction is provided in the embodiment of the present invention
Purposes in attached and degradation of ammonia nitrogen.
Further, the graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst includes graphene/azepine graphite
Alkene and zinc ferrite, the zinc ferrite are distributed in the graphene/azepine graphene layer structure surface or inside, wherein described
Zinc ferrite is spinel structure, and the zinc ferrite has the space Fd3m group structure.
Further, oxonium ion is distributed by face-centred cubic structure in the zinc ferrite crystal, 4 adjacent oxygen from
Subcenter line can get tetrahedral structure and/or adjacent 8 oxonium ions are connected as octahedral structure, and zinc ion occupies tetrahedron
Gap, iron ion occupies octahedral gap.
Further, the mass percent of zinc ferrite is 100-90% in the intelligent photochemical catalyst.
Further, graphene/azepine graphene mass percent is 0%-10% in the intelligent photochemical catalyst.
A kind of preparation of graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst is additionally provided in the embodiment of the present invention
Method comprising following steps: soluble zinc salt, soluble ferric iron salt and graphene/azepine graphene are dissolved in solvent and mixed
Close uniformly, adjusting solution later is alkalinity, then solution is reacted 6-10h under the conditions of 150-200 DEG C, be made the graphene/
Azepine graphene-zinc ferrite intelligence photochemical catalyst.
Further, the molar ratio of the soluble zinc salt and soluble ferric iron salt is 1:1-3.
Further, the soluble zinc salt includes Zn (NO3)2·6H2O, but not limited to this.
Further, the soluble ferric iron salt includes Fe (NO3)3·9H2O, but not limited to this.
Further, the alkaline solution includes NaOH solution, but not limited to this.
This method further include: by reaction kettle be placed in temperature be 180-200 DEG C under conditions of react 8-10h, spend later from
Then sub- water washing places it in drying in the vacuum oven that temperature is 40-80 DEG C, obtains the graphene/azepine
Graphene-zinc ferrite intelligence photochemical catalyst.
Further, the pH value of the sample to be tested is adjusted using 0.1mol/L NaOH solution.
Technology of the invention is further explained below in conjunction with drawings and examples.
Embodiment 1
Graphene oxide (GO) is prepared using improved Hummers method: by 2.0g graphite (99.85%) and 1.0g sodium nitrate
It is put into 500ml beaker, the 50ml concentrated sulfuric acid is added, 6.0g potassium permanganate is slowly added under condition of ice bath, is stirred to react 2h, so
After be warming up to 35 DEG C after continue stir 2h, be then slowly added to the deionized water of 200ml, persistently stir 20min, add
The hydrogen peroxide of 20ml5% restores unreacted potassium permanganate, until after solution becomes glassy yellow continuing that 2h is stirred at room temperature.It will
Reaction system stratification, pours out supernatant, and lower sediment is carried out centrifugal filtration, is washed at least 3 times with 5%HCl, then use
2000ml distilled water washs by several times.By product, dry 6h obtains GO in 60 DEG C of vacuum ovens.
Zinc ferrite (ZnFe2O4) synthesis: 1:2 precise Zn (NO in molar ratio3)2·6H2O(1.7850g,
0.006mol)、Fe(NO3)3·9H2O (4.8480g, 0.012mol) is dissolved separately in 10ml deionized water, precise NaOH
(1.9200g, 0.048mol) is dissolved in 10ml deionized water.NaOH is slowly added dropwise under the conditions of magnetic agitation mixed
It closes in solution, then remaining NaOH in beaker is washed with deionized and adds in mixed solution.Continuing stirring 20min keeps it mixed
It closes uniformly, overall solution volume is about 50ml or so at this time.Then mixed solution is added in the hydrothermal reaction kettle of 100ml, is used
Liquid Residue in deionized water rinse beaker, and be added in reaction kettle, controlling the total volume in reaction kettle is 60ml or so, then
Reaction kettle is placed under conditions of 180 DEG C and reacts 8h, after cooling, take out and stands, be washed with deionized 3-4 times, then will
It dries in its vacuum oven for being placed in 60 DEG C for 24 hours to get sample ZnFe2O4。
Graphene-zinc ferrite (rG-ZnFe2O4) synthesis: 1:2 precise Zn (NO in molar ratio3)2·6H2O
(1.7850g,0.006mol)、Fe(NO3)3·9H2O (4.8480g, 0.012mol) is dissolved separately in 10ml deionized water, then claims
Take GO (0.0868g, ZnFe2O4The 6% of quality) ultrasonic dissolution is in 10ml deionized water, by preceding two under magnetic agitation effect
Person is slowly added in GO solution, and stirring 30min is uniformly mixed.Precise NaOH (1.9200g, 0.048mol) is dissolved in 10ml
In deionized water.NaOH is slowly added dropwise in mixed solution under the conditions of magnetic agitation, then burning is washed with deionized
It remaining NaOH and is added in mixed solution in cup.Continuing stirring 20min is uniformly mixed it, and overall solution volume is about at this time
50ml or so.Then mixed solution is added in the hydrothermal reaction kettle of 100ml, with the Liquid Residue in deionized water rinse beaker,
And be added in reaction kettle, controlling the total volume in reaction kettle is 60ml or so, anti-under conditions of reaction kettle is then placed in 180 DEG C
It answers 8h to take out and stand, be washed with deionized 3-4 times after cooling, then places it in dry in 60 DEG C of vacuum oven
For 24 hours to get sample rG-ZnFe2O4。
The preparation of nessler reagent: accurately weighing 16gNaOH, is dissolved in 40ml water, is sufficiently cooled to room temperature.Weigh 10g HgI2
It is dissolved in 40ml water with 7g KI ultrasonic mixing.Then it is molten this mixed solution to be slowly injected into NaOH under constant agitation
In liquid, 100ml is diluted and be settled to, is sealed in 100ml volumetric flask.The color mechanism of ammonia nitrogen and nessler reagent is as follows:
NH4 ++2[HgI4]2-(Yellow)+4HO-→HgO·Hg(NH2)I(Brown)+7I-+3H2O (1)
The preparation of screening agent: it accurately weighs 50g sodium potassium tartrate tetrahydrate and is dissolved in 100ml in water, heating is boiled, and room is cooled to
Temperature adds water to be settled to 100ml, is sealed in 100ml volumetric flask.
By reagent colorimetric method, the absorption intensity of ammonia nitrogen can be measured at wavelength 388nm, to analyze the dense of ammonia nitrogen
Degree variation carrys out Study of Catalyst degradation of ammonia nitrogen optimum condition.
The degradation of ammonia nitrogen: use 50mL beaker as the reaction unit of photocatalytic degradation ammonia nitrogen, under room temperature (25 DEG C ± 2 DEG C)
Catalysis degeneration experiment is carried out, beaker wall of cup is surrounded with masking foil to avoid stray light emission.It is covered on reactor with filter plate
End, allows visible light λ > 400nm to pass through.The ammonia nitrogen solution of 50ml is packed into reactor, concentration 100mg/L uses Na2CO3-
NaHCO3(0.1mol/L) adjusts the pH of reaction solution as buffer solution, and the rG-ZnFe of about 0.1g is added2O4Catalyst carries out
Catalysis degeneration experiment.The vertical range of reaction solution and light source is about 10cm.The measurement of ammonia-nitrogen content uses Na Shi in reaction process
Reagent colorimetric method.Using ultraviolet-uisible spectrophotometer measurement ammonia nitrogen solution in the suction of wavelength 388nm under nessler reagent colour developing
Receipts degree tracks ammonia nitrogen with this, and referring to Fig. 5, by the degradation of 8h, the degradation rate of ammonia nitrogen is still up to 99%.
Referring to Fig. 1 according to Debye-Scherrer formula: D=k λ/(Wcos θ) calculates to obtain material ZnFe2O4, rG-
ZnFe2O4The average grain diameter of crystal grain be respectively 7.0nm and 7.4nm.
Referring to fig. 2 in 1100cm-1There is NH in left and right4 +Absorption peak, illustrate catalyst by ammonia nitrogen absorption on surface, together
When adsorb ammonia nitrogen and RHB Raman figure, but discovery curve there is new peak, this illustrate catalyst to ammonia nitrogen have selectivity inhale
It is attached.
It is layer structure, ZnFe referring to the TEM image of Fig. 3 graphene2O4Particle Distribution is on the surface of graphene.
The stability of hybrid catalyst, rG-ZnFe are evaluated by multiple circulation experiment referring to fig. 42O4Catalyst is visible
The degradation rate of continuous 8 catalytic degradation ammonia nitrogens under light radiation.Therapy lasted 8h each time passes through after degrading each time
Centrifuge separation, deionized water wash to obtain catalyst, are then further continued for that the catalyst is recycled.In 8 circulation degradation of ammonia nitrogen
Afterwards, ammonia nitrogen removal frank is still 85% or more.
Comparative example 1
Other reaction steps and condition are identical as in embodiment 1, the difference is that:
Ammonia nitrogen solution and the rhodamine B of 50ml is added in the experiment of photocatalysis to selectively degradation of ammonia nitrogen in reactor simultaneously
(wherein, the concentration of ammonia nitrogen is 100mg/L, and the concentration of rhodamine B is 100mg/L), is measured using ultraviolet-uisible spectrophotometer
The trap of solution, referring to Fig. 6, the degradation rate by 8 hours degradation process rhodamine Bs is only 40%, remaining dense in system
Degree is still greater than 60mg/L, and the degradation rate of ammonia nitrogen is still greater than 95%,.
Comparative example 2
Other reaction steps and condition are identical as in embodiment 1, the difference is that:
The ammonia nitrogen solution and methyl orange (its of 50ml is added in the experiment of photocatalysis to selectively degradation of ammonia nitrogen in reactor simultaneously
In, the concentration of ammonia nitrogen is 100mg/L, and the concentration of methyl orange is 100mg/L), solution is measured using ultraviolet-uisible spectrophotometer
Trap, referring to Fig. 7, the degradation rate by 8 hours degradation process rhodamine Bs is only 30%, and residual concentration is still in system
Greater than 70mg/L, and the degradation rate of ammonia nitrogen is still greater than 95%.
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 (8)
1. the purposes of graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst selective absorption and photocatalysis denitrogenation, feature
Be: the graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst includes graphene and/or azepine graphene and ferrous acid
Zinc, the mass percentage content of the zinc ferrite are the quality hundred of >=90% and < 100%, graphene and/or azepine graphene
Point than content be > 0% and≤10%, the zinc ferrite is distributed in the layer structure table of the graphene and/or azepine graphene
Face and/or inside, wherein the zinc ferrite is spinel structure, and the zinc ferrite has the space Fd3m group structure, wherein
Oxonium ion is distributed by face-centred cubic structure, and 4 adjacent oxonium ion lines of centres can get tetrahedral structure and/or adjacent
8 oxonium ions are connected as octahedral structure, and zinc ion occupies tetrahedral gap, and iron ion occupies octahedral gap；It is described
Purposes include: that the water body containing ammonia nitrogen is added in the intelligent photochemical catalyst and forms mixed system, and adjusts the mixing
The pH value of system is greater than 9, then with mixed system described in radiation of visible light, the ammonia nitrogen in water body is made to be degraded to N2Gas realizes water
The removing of ammonia nitrogen in body.
2. purposes according to claim 1, characterized by comprising: the mixed system is adjusted to pH value and is greater than
10.5, then with mixed system described in radiation of visible light, realize the removing of ammonia nitrogen in water body.
3. purposes according to claim 1, which is characterized in that the graphene/azepine graphene-zinc ferrite intelligence light is urged
The preparation method of agent includes: that soluble zinc salt, soluble ferric iron salt and graphene or azepine graphene are dissolved in solvent to mix
It closes uniformly, adjusts the mixed solution later as alkalinity, then the mixed solution is reacted into 6-10h under the conditions of 150-200 DEG C,
The graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst is made.
4. purposes according to claim 3, it is characterised in that: the molar ratio of the soluble zinc salt and soluble ferric iron salt is
1:1-3.
5. purposes according to claim 3, it is characterised in that: the soluble zinc salt includes Zn (NO3)2·6H2O。
6. purposes according to claim 3, it is characterised in that: the soluble ferric iron salt includes Fe (NO3)3·9H2O。
7. purposes according to claim 3, it is characterised in that: to adjust the alkaline solution of the mixed solution to alkalinity
Including NaOH solution.
8. purposes according to claim 3, characterized by comprising: it is 180-200 that the mixed solution, which is placed in temperature,
8-10h is reacted under conditions of DEG C, is washed with deionized later, and the vacuum oven that temperature is 40-80 DEG C is then placed it in
Interior drying obtains the graphene/azepine graphene-zinc ferrite intelligence photochemical catalyst.
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| CN103871755A (en) * | 2014-03-05 | 2014-06-18 | 南京理工大学 | N-doped graphene/nickel ferrite nanometer compound material and preparation thereof |
| CN103864010A (en) * | 2014-03-05 | 2014-06-18 | 南京理工大学 | Nitrogen-doped graphene/cobalt ferrite nano composite material and preparation method thereof |
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