CN106964388A - A kind of preparation method of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping - Google Patents
A kind of preparation method of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping Download PDFInfo
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- CN106964388A CN106964388A CN201710126313.5A CN201710126313A CN106964388A CN 106964388 A CN106964388 A CN 106964388A CN 201710126313 A CN201710126313 A CN 201710126313A CN 106964388 A CN106964388 A CN 106964388A
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- wolframic acid
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- 239000002253 acid Substances 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 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 37
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 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 7
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 7
- 235000010855 food raising agent Nutrition 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 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
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001868 water Inorganic materials 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
- 238000003756 stirring Methods 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 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 abstract description 4
- 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
- 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
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007974 melamines Chemical class 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
- 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
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
-
- 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
- C02F1/30—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
-
- 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
-
- 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
Abstract
The present invention relates to a kind of preparation of two-dimentional graphite phase carbon nitride (g C3N4) composite photo-catalyst of wolframic acid stannous (α SnWO4) doping, including step：The preparation of wolframic acid stannous (α SnWO4), the preparation of two-dimentional graphite phase carbon nitride (g C3N4) and the preparation of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping.The beneficial effects of the invention are as follows：The composite photo-catalyst preparation process is succinct and condition is easily controllable.Tested according to structural characterization and performance characterization, it can be found that the prepared two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping has chemical property stable, pattern is uniform, the advantages of high catalytic efficiency, again because there is raw material to be easy to get for it, and the advantages of prepare with low cost, so it has certain research and application value.
Description
Technical field
Prepared the invention belongs to nano material and applied technical field, be 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 technology
With the progress of industry, problem of environmental pollution is increasingly serious.Photocatalysis technology is used as a kind of new environmental pollution
Governing measure is gradually to cause the widely studied of domestic and international scientist.And the development and utilization of new 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 the advantages that chemical property is stable, inexpensive, nontoxic.At present, 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, grind
Study carefully and show single component g-C3N4Photochemical catalyst but has that solar energy utilization ratio is low, and photo-generate electron-hole recombination rate is high, amount
The sub- low problem of efficiency.These problems greatly limit g-C3N4The application of photochemical catalyst and development.Therefore, in recent years, photocatalysis
The photocatalysis performance study on the modification of agent gradually turn into photocatalysis subject in focus.The method of modifying being currently known includes：It is expensive
The methods such as the methods such as metal deposit, semiconductors coupling, nonmetal doping, limellar stripping and pore structure.Research discovery, class graphite
Phase carbon nitride has what a kind of sheet azotized carbon nano piece was stacked, if successfully the sheet of these stackings can be peeled away
The specific surface area of class graphite phase carbon nitride then can be effectively improved, while the avtive spot of increase carbonitride, reduces photoproduction
Carrier recombination efficiency, so as to improve the photocatalysis performance of carbonitride.In addition, by two kinds of semiconductors be combined it is composite modified
Method highly effective can improve light induced electron and hole separative efficiency, so that the photocatalysis performance of single catalyst is improved, finally,
Improve photocatalysis efficiency.If in addition, limellar stripping is combined with building compound system method, can must efficiently improve class stone
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 tool
Have narrow band gap energy, the advantage such as wider visible light-responded scope, abundant raw materials, gradually studied in photocatalysis field
The attention of person.But single wolframic acid stannous photochemical catalyst has that photocatalysis efficiency is low, 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 new composite photo-catalyst of compound structure, can not only be adsorbed with carbonitride and the optical Response of wolframic acid stannous
Performance, specific surface area more can effectively improve the separative efficiency of photohole, and then improve photocatalysis performance.Therefore, study
It is very significant with this new composite photo-catalyst is developed.At present, this new wolframic acid stannous doped graphite phase
Nitridation carbon composite photocatalyst does not have relevant report.
The content of the invention
The technical problem to be solved in the present invention is：Based on above mentioned problem, 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 scheme being used of its technical problem：A kind of two-dimentional graphite-phase of wolframic acid stannous doping
The preparation method of carbon composite photocatalyst is nitrogenized, is comprised the following steps：
(1) two-dimentional graphite phase carbon nitride (g-C3N4) preparation：Crucible is put into after carbon nitrogen source is well mixed with leavening agent
In, 450~550 DEG C are heated to, 4~6h is heated, naturally cools to and product is obtained after grinding at room temperature；
(2) wolframic acid stannous (α-SnWO4) preparation：By dichloro stannous (SnCl2) it is dissolved in the formation solution of 20~50ml solvents I
A, then by sodium tungstate (NaWO4.H2) and cetyl trimethylammonium bromide (CTAB) is being dissolved in the formation of 20~50ml solvents I respectively O
Solution B.B is added dropwise in A dropwise, pH to 7~8 is adjusted with 10mol/L NaOH solution, 20~60min is stirred, it is rear to move into instead
180~200 DEG C of 12~24h of reaction, centrifugation in kettle are answered, washs in 60~80 DEG C of dry 12~24h, wolframic acid stannous is obtained after grinding
(α-SnWO4)；
(3) wolframic acid stannous (SnWO4) the two-dimentional graphite phase carbon nitride (g-C of doping3N4) composite photo-catalyst preparation：Will step
Suddenly in (1) dried certain mass two-dimentional graphite phase carbon nitride (g-C3N4) and wolframic acid stannous (SnWO4) it is separately added into beaker
In, it is put into 30ml dispersants, ultrasonic 2h.Then by SnWO4Suspension is added dropwise to the suspension of two-dimentional graphite-phase nitridation dropwise
In, 12h is stirred, 120 DEG C of autoclave is shifted, 4h is reacted.Centrifugal filtration it is dry product.
Further, carbon nitrogen source is urea, dicyandiamide, cyanamide, melamine etc., leavening agent in described step (1)
For ammonium chloride, ammonium bromide or ammonium nitrate etc..
Further, solvent I is deionized water or ethylene glycol, ethanol etc. in described step (2)；Described step (3)
Middle dispersant is deionized water or ethanol.
Further, the quality of carbon nitrogen source is 5~10g in described 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 in described step (2):1.5 or 1:2；Stannous chloride and ten
The amount ratio of six alkyl trimethyl ammonium bromides (CTAB) material is 6:1 or 5:1.
Further, the quality of wolframic acid stannous is that two-dimentional graphite phase carbon nitride mass ratio is 1 in described step (3):10
Or 10:1.
Further, the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping in described step (3)
Preparation method, it is characterized in that：12h is stirred, hydrothermal temperature is 120 DEG C, reaction time 6h.
The beneficial effects of the invention are as follows：The composite photo-catalyst prepared by this method has preferable stability, without two
Secondary pollution, and catalytic efficiency, can in 80min in the clearance of target contaminant rhodamine B up to 90.37%.In addition, this is multiple
The preparation method of closing light catalyst has simple, and preparation condition is easily controllable, the advantages of non-secondary pollution.Thus have necessarily
Research and application value.
Brief description of the drawings
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is the sour stannous of pure tungsten and the two-dimentional graphite phase carbon nitride of wolframic acid stannous doping that the embodiment of the present invention 1 is prepared
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, pure tungsten acid stannous and the two-dimentional graphite of wolframic acid stannous doping
The X-ray diffractogram of phase carbon nitride composite photo-catalyst；
Fig. 3 is the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping that the embodiment of the present invention 1 is prepared
The ultraviolet-visible absorption spectroscopy of rhodamine B degradation is with light application time variation diagram.
Embodiment
Presently in connection with specific embodiment, the invention will be further described, following examples be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1
(1) graphite phase carbon nitride (g-C3N4) preparation：5g melamines are well mixed with 10 grams of leavening agents and are put into crucible
In, 450 DEG C are heated in Muffle furnace, 4h is heated, naturally cools to and product is obtained after grinding at room temperature；
(2) wolframic acid stannous (α-SnWO4) preparation：By 1.8g dichloro stannous (SnCl2) be dissolved in 20ml ethanol and form solution
A, then by 2.7g sodium tungstates (NaWO4.H2) and 0.3g cetyl trimethylammonium bromides (CTAB) are respectively in 20ml water is dissolved in O
Form solution B.B is added dropwise in A dropwise, pH to 7 is adjusted with 10mol/L NaOH solution, 20min is stirred, it is rear to move into reaction
180 DEG C of reaction 12h, centrifugation, are washed in 60 DEG C of dry 12h in kettle, and wolframic acid stannous (α-SnWO are obtained after grinding4)；
(3) preparation of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping：By 10g two dimensions in step (1)
Graphite phase carbon nitride and 1g wolframic acid stannous are separately added into beaker, are put into 30ml dispersants, ultrasonic 2h.Then by SnWO4It is outstanding
Turbid liquid is added dropwise in the suspension of two-dimentional graphite-phase nitridation dropwise, is stirred 12h, is shifted 120 DEG C of autoclave, reacts 4h.Centrifuged
It is filtered dry dry product.
1st, the pattern and compound mensuration of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping
The two-dimentional stone of wolframic acid stannous doping prepared by embodiment 1 is observed using Japanese JSM-6360A types SEM
The pattern of black phase carbon nitride composite photo-catalyst, scanning electron microscope (SEM) photograph are as shown in figure 1, as can be seen from Fig., prepared by present embodiment
The pattern of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping be that two-dimentional graphite phase carbon nitride area load has
Granular wolframic acid stannous nano particle, and be distributed more uniform.
The sour stannous of pure tungsten, pure carbonitride and wolframic acid stannous/two dimension graphite phase carbon nitride complex light prepared by embodiment 1
The crystal phase structure of catalyst is analyzed by Rigaku D/max2500PC rotations x-ray diffractometer, wherein, X-ray is Cu targetsVoltage 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 patterns of preparation as shown in Fig. 2 as seen from the figure
See at 25.06 °, 31.84 °, 32.94 °, 36.3 °, 52.76 °, 57.46 ° and 60.86 ° the feature diffraction of wolframic acid stannous occur
Peak corresponds to (111) (200) (210) (002) (161) (232) and (123) crystal face of wolframic acid stannous, 12.78 ° and 27.8 ° respectively
It is that the characteristic diffraction peak of two-dimentional graphite phase carbon nitride corresponds to (100) and (002) crystal face of carbonitride respectively.It therefore, it can prove
Two-dimentional graphite phase carbon nitride and wolframic acid stannous are comprised only in the composite photo-catalyst, and does not change the two in recombination process
Chemical constitution and crystal formation.
2nd, the photocatalysis performance and potential application of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping
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, take wolframic acid stannous/two dimension graphite phase carbon nitride composite photo-catalyst 25mg, first dark
Reaction 30min reaches that adsorption-desorption is balanced, then carries out visible light catalytic reaction, using 1000w xenon lamps as light source, every certain
Time extracts 5ml reaction solutions with dropper, is put into supercentrifuge and centrifuges 4 minutes, and the light degradation situation of rhodamine B utilizes ultraviolet
Visible spectrophotometer is detected.
The degradability of wolframic acid stannous/two dimension graphite phase carbon nitride composite photo-catalyst prepared by embodiment 1 to rhodamine B
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 has higher photocatalytic activity.
Claims (6)
1. a kind of preparation method of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping, it is characterized in that：Including with
Lower step：
(1) two-dimentional graphite phase carbon nitride (g-C3N4) preparation：It is put into after carbon nitrogen source is well mixed with leavening agent in crucible, plus
Heat heats 4~6h, naturally cools to and product is obtained after grinding at room temperature to 450~550 DEG C；
(2) wolframic acid stannous (α-SnWO4) preparation：By dichloro stannous (SnCl2) the formation solution A of 20~50ml solvents I is dissolved in, then
By sodium tungstate (NaWO4.H2O) and cetyl trimethylammonium bromide (CTAB) respectively be dissolved in 20~50ml solvents I formation solution
B.B is added dropwise in A dropwise, pH to 7~8 is adjusted with 10mol/L NaOH solution, stirs 20~60min, reactor is moved into afterwards
In 180~200 DEG C reaction 12~24h, centrifugation, wash in 60~80 DEG C of drys 12~24h, after grinding obtain wolframic acid stannous (α-
SnWO4)；
(3) wolframic acid stannous (α-SnWO4) the two-dimentional graphite phase carbon nitride (g-C of doping3N4) composite photo-catalyst preparation：By step
(1) the two-dimentional graphite phase carbon nitride (g-C of dried certain mass in3N4) and wolframic acid stannous (α-SnWO4) it is separately added into beaker
In, it is put into 30ml dispersants, ultrasonic 2h.Then by SnWO4Suspension is added dropwise to the suspension of two-dimentional graphite-phase nitridation dropwise
In, 12h is stirred, 120 DEG C of autoclave is shifted, 6h is reacted.Centrifugal filtration it is dry product.
2. a kind of preparation side of two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping according to claim 1
Method, it is characterized in that：Carbon nitrogen source is urea, dicyandiamide, cyanamide, melamine etc. in described step (1), and leavening agent is chlorination
Ammonium, ammonium bromide or ammonium nitrate etc..
3. a kind of preparation side of two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping according to claim 1
Method, it is characterized in that：Solvent I is deionized water or ethylene glycol, ethanol etc. in described step (2)；Disperse in described step (3)
Agent is deionized water or ethanol.
4. a kind of preparation side of two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping according to claim 1
Method, it is characterized in that：The quality of carbon nitrogen source is 5~10g in described step (1), and 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 in described step (2):1.5 or 1:2；Stannous chloride and hexadecane
The amount ratio of base trimethylammonium bromide (CTAB) material is 6:1 or 5:1.
5. a kind of preparation side of two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping according to claim 1
Method, it is characterized in that：The quality of wolframic acid stannous is that two-dimentional graphite phase carbon nitride mass ratio is 1 in described step (3):10 or 10:
1。
6. a kind of preparation side of two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping according to claim 1
Method, it is characterized in that：12h is stirred, hydrothermal temperature is 120 DEG C, reaction time 6h.
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| CN107352519A (en) * | 2017-08-01 | 2017-11-17 | 江苏理工学院 | A kind of C3N4The preparation method of nano wire |
| CN108906099A (en) * | 2018-05-30 | 2018-11-30 | 常州科力尔环保科技有限公司 | Cu2S/g-C3N4The preparation method of heterojunction photocatalyst |
| CN114160179A (en) * | 2021-12-08 | 2022-03-11 | 衡阳师范学院 | Preparation and application of graphite-phase carbon nitride and stannous tungstate composite photocatalyst |
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| CN103934012A (en) * | 2014-04-14 | 2014-07-23 | 大连民族学院 | SnS2/g-C3N4 composite nanosheet photocatalyst and preparation method thereof |
| 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 |
| CN106076389A (en) * | 2016-06-15 | 2016-11-09 | 常州大学 | The preparation method and application of bismuth molybdate/graphite phase carbon nitride composite catalyst |
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| CN103934012A (en) * | 2014-04-14 | 2014-07-23 | 大连民族学院 | SnS2/g-C3N4 composite nanosheet photocatalyst and preparation method thereof |
| 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 |
| CN106076389A (en) * | 2016-06-15 | 2016-11-09 | 常州大学 | The preparation method and application of bismuth molybdate/graphite phase carbon nitride composite catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107352519A (en) * | 2017-08-01 | 2017-11-17 | 江苏理工学院 | A kind of C3N4The preparation method of nano wire |
| CN108906099A (en) * | 2018-05-30 | 2018-11-30 | 常州科力尔环保科技有限公司 | Cu2S/g-C3N4The preparation method of heterojunction photocatalyst |
| CN114160179A (en) * | 2021-12-08 | 2022-03-11 | 衡阳师范学院 | Preparation and application of graphite-phase carbon nitride and stannous tungstate composite photocatalyst |
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