CN106964388B - A kind of wolframic acid stannous adulterates the preparation method of two-dimentional graphite phase carbon nitride composite photo-catalyst - Google Patents
A kind of wolframic acid stannous adulterates the preparation method of two-dimentional graphite phase carbon nitride composite photo-catalyst Download PDFInfo
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- wolframic acid
- carbon nitride
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- acid stannous
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- 239000002253 acid Substances 0.000 title claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000010439 graphite Substances 0.000 title claims abstract description 46
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 235000010855 food raising agent Nutrition 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000012512 characterization method Methods 0.000 abstract 2
- 230000001699 photocatalysis Effects 0.000 description 15
- 238000007146 photocatalysis Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 10
- 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 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- XYZSNCGFOMVMIA-UHFFFAOYSA-N 1,3-dioxa-2$l^{2}-stanna-4$l^{6}-tungstacyclobutane 4,4-dioxide Chemical compound O=[W]1(=O)O[Sn]O1 XYZSNCGFOMVMIA-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- 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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Abstract
The present invention relates to the preparations that a kind of wolframic acid stannous (α-SnWO4) adulterates two-dimentional graphite phase carbon nitride (g-C3N4) composite photo-catalyst, comprising steps of the preparation of wolframic acid stannous (α-SnWO4), the preparation of two-dimentional graphite phase carbon nitride (g-C3N4) and wolframic acid stannous adulterate the preparation of two-dimentional graphite phase carbon nitride composite photo-catalyst.The beneficial effects of the present invention are: the composite photo-catalyst preparation process is succinct and condition is easily controllable.It is tested according to structural characterization and performance characterization, stablize it can be found that prepared wolframic acid stannous adulterates two-dimentional graphite phase carbon nitride composite photo-catalyst with chemical property, pattern is uniform, the advantages that high catalytic efficiency, it is easy to get again because of it with raw material, and preparation cost it is cheap the advantages that, so it is with certain research and application value.
Description
Technical field
The invention belongs to nano material preparation and applied technical fields, are related to a kind of two-dimentional graphite-phase nitrogen of wolframic acid stannous doping
Change the preparation and its application of carbon composite photocatalyst.
Background technique
With the progress of industry, environmental pollution is getting worse.Photocatalysis technology is as a kind of novel environmental pollution
Governing measure is gradually to cause the extensive research of domestic and international scientist.And the development and utilization of novel effective photochemical catalyst
It is the foundation stone for moving towards industrialization of photocatalysis technology.In numerous photochemical catalysts, graphite phase carbon nitride (g-C3N4) as a kind of
The organic polymer photochemical catalyst of novel visible response has many advantages, such as that chemical property is stable, inexpensive, nontoxic.Currently, its
It has been widely studied in research fields such as photocatalytic degradation, photocatalysis hydrogen productions, and has obtained a series of marked achievements.But it grinds
Study carefully and shows single component g-C3N4Photochemical catalyst but to there is solar energy utilization ratio low, photo-generate electron-hole recombination rate is high, amount
The problems such as sub- low efficiency.These problems greatly limit g-C3N4Application and the development of photochemical catalyst.Therefore, in recent years, photocatalysis
The photocatalysis performance study on the modification of agent gradually become photocatalysis subject in hot spot.The method of modifying being currently known includes: expensive
Metal deposit, semiconductors coupling, nonmetal doping, the methods of the methods of limellar stripping and pore structure.The study found that class graphite
Made of there is phase carbon nitride a kind of sheet azotized carbon nano piece to stack, if successfully these sheets stacked can be peeled away
The specific surface area of class graphite phase carbon nitride then can be effectively improved, and at the same time increasing the active site of carbonitride, reduces photoproduction
Carrier recombination efficiency, to improve the photocatalysis performance of carbonitride.In addition, two kinds of semiconductors are carried out compound composite modified
The highly effective raising light induced electron of method energy and hole separative efficiency, so that the photocatalysis performance of single catalyst is improved, finally,
Improve photocatalysis efficiency.In addition, can must efficiently improve class stone if limellar stripping is combined with building compound system method
The photocatalysis efficiency of black phase carbon nitride.
In recent years, research finds wolframic acid stannous (α-SnWO4) it is used as a kind of tungstates (AWO4Type) photochemical catalyst, and have
Have the advantages such as narrow band gap energy, wider visible light-responded range, abundant raw materials, gradually studied in photocatalysis field
The attention of person.But that there are photocatalysis efficiencies is low for single wolframic acid stannous photochemical catalyst, and specific surface area is small, and absorption property difference etc. lacks
Point.Therefore, we are based on synthesizing two-dimentional class graphite phase carbon nitride and wolframic acid stannous, by two-dimentional class graphite phase carbon nitride and tungsten
Sour stannous carries out the novel composite photo-catalyst of compound building, can not only be adsorbed with the optical Response of carbonitride and wolframic acid stannous
Performance, specific surface area more can effectively improve the separative efficiency of photohole, and then improve photocatalysis performance.Therefore, it studies
It is very significant with this novel composite photo-catalyst is developed.Currently, this novel wolframic acid stannous doped graphite phase
Nitridation carbon composite photocatalyst does not have relevant report.
Summary of the invention
The technical problem to be solved by the present invention is based on the above issues, the present invention provides a kind of wolframic acid stannous doping two dimension
The preparation method of graphite phase carbon nitride composite photo-catalyst.
The present invention solves a technical solution used by its technical problem: a kind of two-dimentional graphite-phase of wolframic acid stannous doping
Nitrogenize the preparation method of carbon composite photocatalyst, comprising the following steps:
(1) two-dimentional graphite phase carbon nitride (g-C3N4) preparation: carbon nitrogen source and leavening agent are put into crucible after mixing
In, 450~550 DEG C are heated to, 4~6h is heated, obtains product after cooled to room temperature grinding；
(2) wolframic acid stannous (α-SnWO4) preparation: by dichloro stannous (SnCl2) it is dissolved in the formation solution of 20~50ml solvent I
A, then by sodium tungstate (NaWO4.H2O) and cetyl trimethylammonium bromide (CTAB) is being dissolved in the formation of 20~50ml solvent I respectively
Solution B.B is added dropwise in A dropwise, pH to 7~8 is adjusted with the NaOH solution of 10mol/L, stirs 20~60min, it is rear to move into instead
Answer in kettle 180~200 DEG C of reactions 12~for 24 hours, centrifugation, washing in 60~80 DEG C dry 12~for 24 hours, after grinding wolframic acid stannous
(α-SnWO4)；
(3) wolframic acid stannous (SnWO4) adulterate two-dimentional graphite phase carbon nitride (g-C3N4) composite photo-catalyst preparation: will walk
Suddenly the two-dimentional graphite phase carbon nitride (g-C of the certain mass in (1) after drying3N4) and wolframic acid stannous (SnWO4) it is separately added into beaker
In, it is put into 30ml dispersing agent, ultrasonic 2h.Then by SnWO4Suspension is added dropwise to the suspension of two-dimentional graphite-phase nitridation dropwise
In, 12h is stirred, shifts 120 DEG C of autoclave, reacts 4h.Centrifugal filtration it is dry product.
Further, carbon nitrogen source is urea, dicyandiamide, cyanamide, melamine etc., leavening agent in the step (1)
For ammonium chloride, ammonium bromide or ammonium nitrate etc..
Further, solvent I is deionized water or ethylene glycol, ethyl alcohol etc. in the step (2)；The step (3)
Middle dispersing agent is deionized water or ethyl alcohol.
Further, the quality of carbon nitrogen source is 5~10g in the step (1), and leavening agent quality is carbon nitrogen source quality
2~3 times；The mass ratio of the quality of stannous chloride and sodium tungstate is 1:1.5 or 1:2 in the step (2)；Stannous chloride and ten
Six alkyl trimethyl ammonium bromides (CTAB) the mass ratio of the material is 6:1 or 5:1.
Further, it is 1:10 that the quality of wolframic acid stannous, which is two-dimentional graphite phase carbon nitride mass ratio, in the step (3)
Or 10:1.
Further, the wolframic acid stannous in the step (3) adulterates two-dimentional graphite phase carbon nitride composite photo-catalyst
Preparation method, it is characterized in that: stirring 12h, hydrothermal temperature is 120 DEG C, reaction time 6h.
The beneficial effects of the present invention are: there is preferable stability by composite photo-catalyst prepared by this method, without two
Secondary pollution, and catalytic efficiency, can in 80min in the removal rate of target contaminant rhodamine B up to 90.37%.In addition, this is multiple
The advantages that preparation method of light combination catalyst has simply, and preparation condition is easily controllable, without secondary pollution.Thus have centainly
Research and application value.
Detailed description of the invention
The following further describes the present invention with reference to the drawings.
Fig. 1 is that the pure tungsten acid stannous that the embodiment of the present invention 1 is prepared and wolframic acid stannous adulterate two-dimentional graphite phase carbon nitride
The scanning electron microscope (SEM) photograph of composite photo-catalyst；
Fig. 2 is the pure carbonitride that the embodiment of the present invention 1 is prepared, and pure tungsten acid stannous and wolframic acid stannous adulterate two-dimentional graphite
The X-ray diffractogram of phase carbon nitride composite photo-catalyst；
Fig. 3 is that the wolframic acid stannous that the embodiment of the present invention 1 is prepared adulterates two-dimentional graphite phase carbon nitride composite photo-catalyst
The ultraviolet-visible absorption spectroscopy of rhodamine B degradation is with light application time variation diagram.
Specific embodiment
Presently in connection with specific embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1
(1) graphite phase carbon nitride (g-C3N4) preparation: 5g melamine is uniformly mixed with 10 grams of leavening agents and is put into crucible
In, it is heated to 450 DEG C in Muffle furnace, heats 4h, obtains product after cooled to room temperature grinding；
(2) wolframic acid stannous (α-SnWO4) preparation: by 1.8g dichloro stannous (SnCl2) be dissolved in 20ml ethyl alcohol and form solution
A, then by 2.7g sodium tungstate (NaWO4.H2O) and 0.3g cetyl trimethylammonium bromide (CTAB) is respectively in being dissolved in 20ml water
Form solution B.B is added dropwise in A dropwise, pH to 7 is adjusted with the NaOH solution of 10mol/L, stirs 20min, it is rear to move into reaction
180 DEG C of reaction 12h in kettle, centrifugation wash in 60 DEG C of dry 12h, wolframic acid stannous (α-SnWO are obtained after grinding4)；
(3) wolframic acid stannous adulterates the preparation of two-dimentional graphite phase carbon nitride composite photo-catalyst: by 10g two dimension in step (1)
Graphite phase carbon nitride and 1g wolframic acid stannous are separately added into beaker, are put into 30ml dispersing agent, ultrasonic 2h.Then by SnWO4It is outstanding
Turbid is added dropwise to dropwise in the suspension of two-dimentional graphite-phase nitridation, is stirred 12h, is shifted 120 DEG C of autoclave, reacts 4h.It was centrifuged
It is filtered dry dry product.
1, wolframic acid stannous adulterates the pattern and compound mensuration of two-dimentional graphite phase carbon nitride composite photo-catalyst
Two-dimentional stone is adulterated using wolframic acid stannous prepared by Japanese JSM-6360A type scanning electron microscope observation embodiment 1
The pattern of black phase carbon nitride composite photo-catalyst, scanning electron microscope (SEM) photograph is as shown in Figure 1, as can be seen from Fig., prepared by present embodiment
Wolframic acid stannous to adulterate the pattern of two-dimentional graphite phase carbon nitride composite photo-catalyst be that two-dimentional graphite phase carbon nitride area load has
Granular wolframic acid stannous nano particle, and be distributed more uniform.
Pure tungsten acid stannous, pure carbonitride prepared by embodiment 1 and wolframic acid stannous/two dimension graphite phase carbon nitride complex light
The crystal phase structure of catalyst is analyzed by Rigaku D/max2500PC rotation x-ray diffractometer, wherein X-ray is Cu targetVoltage 40kV, electric current 100mA, step-length are 0.02 °, 5 °~80 ° of scanning range.X-ray diffractogram
Spectrum, can in wolframic acid stannous/two dimension graphite phase carbon nitride composite photo-catalyst XRD diffraction pattern of preparation as shown in Fig. 2, as seen from the figure
See the feature diffraction of wolframic acid stannous occur at 25.06 °, 31.84 °, 32.94 °, 36.3 °, 52.76 °, 57.46 ° and 60.86 °
Peak respectively corresponds (111) (200) (210) (002) (161) (232) and (123) crystal face of wolframic acid stannous, 12.78 ° with 27.8 °
It is that the characteristic diffraction peak of two-dimentional graphite phase carbon nitride respectively corresponds (100) and (002) crystal face of carbonitride.Therefore, it can prove
Two-dimentional graphite phase carbon nitride and wolframic acid stannous are contained only in the composite photo-catalyst, and the two is had not been changed in recombination process
Chemical structure and crystal form.
2, wolframic acid stannous adulterates the photocatalysis performance and potential application of two-dimentional graphite phase carbon nitride composite photo-catalyst
Research
The wolframic acid stannous prepared in embodiment 1/two dimension graphite phase carbon nitride composite photocatalyst for degrading rhodamine B is molten
Liquid, wherein rhodamine B solution concentration 10mg/L, takes wolframic acid stannous/two dimension graphite phase carbon nitride composite photo-catalyst 25mg, first dark
Reaction 30min reaches adsorption-desorption balance, then carries out visible light catalytic reaction, uses 1000w xenon lamp as light source, every certain
Time extracts 5ml reaction solution with dropper, is put into supercentrifuge and is centrifuged 4 minutes, and the light degradation situation of rhodamine B utilizes ultraviolet
Visible spectrophotometer detection.
Degradability of the stannous of wolframic acid prepared by the embodiment 1/two dimension graphite phase carbon nitride composite photo-catalyst to rhodamine B
It can be as shown in Figure 3.As seen from Figure 3, in 80min rhodamine B degradation rate to reach 90.37%, it is seen that prepared wolframic acid is sub-
Tin/two dimension graphite phase carbon nitride composite photo-catalyst photocatalytic activity with higher.
Claims (5)
1. a kind of wolframic acid stannous adulterates the preparation method of two-dimentional graphite phase carbon nitride composite photo-catalyst, it is characterized in that: include with
Lower step:
(1) two-dimentional graphite phase carbon nitride (g-C3N4) preparation: carbon nitrogen source and leavening agent are put into crucible after mixing, added
Heat heats 4~6h, obtains product after cooled to room temperature grinding to 450~550 DEG C；
(2) wolframic acid stannous α-SnWO4Preparation: by stannous chloride (SnCl2) it is dissolved in the formation solution A of 20~50mL solvent I, then will
Sodium tungstate (NaWO4·H2O) it is dissolved in 20~50mL solvent I respectively and forms solution B with cetyl trimethylammonium bromide (CTAB),
B is added dropwise in A dropwise, pH to 7~8 is adjusted with the NaOH solution of 10mol/L, is moved into reaction kettle after stirring 20~60min
180~200 DEG C of reactions 12~for 24 hours, centrifugation, washing in 60~80 DEG C dry 12~for 24 hours, after grinding wolframic acid stannous α-SnWO4；
(3) wolframic acid stannous α-SnWO4Adulterate two-dimentional graphite phase carbon nitride (g-C3N4) composite photo-catalyst preparation: by step (1)
Two-dimentional graphite phase carbon nitride (the g-C of certain mass after middle drying3N4) and wolframic acid stannous α-SnWO4It is separately added into beaker, puts
Enter in 30mL dispersing agent, ultrasonic 2h, then by SnWO4Suspension is added dropwise to dropwise in the suspension of two-dimentional graphite phase carbon nitride,
Stir 12h, shift 120 DEG C of autoclave, react 6h, centrifugal filtration it is dry product.
2. the preparation side that a kind of wolframic acid stannous according to claim 1 adulterates two-dimentional graphite phase carbon nitride composite photo-catalyst
Method, it is characterized in that: carbon nitrogen source is urea, dicyandiamide, cyanamide, melamine in the step (1), leavening agent is chlorination
Ammonium, ammonium bromide or ammonium nitrate.
3. the preparation side that a kind of wolframic acid stannous according to claim 1 adulterates two-dimentional graphite phase carbon nitride composite photo-catalyst
Method, it is characterized in that: solvent I is deionized water or ethylene glycol, ethyl alcohol in the step (2)；Dispersing agent in the step (3)
For deionized water or ethyl alcohol.
4. the preparation side that a kind of wolframic acid stannous according to claim 1 adulterates two-dimentional graphite phase carbon nitride composite photo-catalyst
Method, it is characterized in that: the quality of carbon nitrogen source is 5~10g in the step (1), leavening agent quality is the 2~3 of carbon nitrogen source quality
Times；The mass ratio of the quality of stannous chloride and sodium tungstate is 1:1.5 or 1:2 in the step (2)；Stannous chloride and hexadecane
Base trimethylammonium bromide (CTAB) the mass ratio of the material is 6:1 or 5:1.
5. the preparation side that a kind of wolframic acid stannous according to claim 1 adulterates two-dimentional graphite phase carbon nitride composite photo-catalyst
Method, it is characterized in that: the quality of wolframic acid stannous and two-dimentional graphite phase carbon nitride mass ratio are 1:10 or 10 in the step (3):
1。
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| WO2015196738A1 (en) * | 2014-06-25 | 2015-12-30 | 华南理工大学 | Carbon nitride-modified titanium dioxide super-hydrophilic porous film and preparation method and use thereof |
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