CN108607588A - A kind of preparation method of La doped class graphite phase carbon nitride catalysis material - Google Patents
A kind of preparation method of La doped class graphite phase carbon nitride catalysis material Download PDFInfo
- Publication number
- CN108607588A CN108607588A CN201810252117.7A CN201810252117A CN108607588A CN 108607588 A CN108607588 A CN 108607588A CN 201810252117 A CN201810252117 A CN 201810252117A CN 108607588 A CN108607588 A CN 108607588A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- phase carbon
- class graphite
- graphite phase
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 82
- 239000010439 graphite Substances 0.000 title claims abstract description 82
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002086 nanomaterial Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 239000013049 sediment Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000002242 deionisation method Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 5
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 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 abstract description 4
- 229940012189 methyl orange Drugs 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 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 abstract description 4
- 229940043267 rhodamine b Drugs 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000005297 material degradation process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 20
- 238000006731 degradation reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 14
- 229910052746 lanthanum Inorganic materials 0.000 description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- XWFVFZQEDMDSET-UHFFFAOYSA-N gadolinium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XWFVFZQEDMDSET-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent 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
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011787 zinc oxide Substances 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of La doped class graphite phase carbon nitride catalysis material prepares La doped class graphite phase carbon nitride catalysis material using lanthanum nitrate hexahydrate, melamine and ethylene glycol as primary raw material using the method for solvent-thermal process.In visible light（λ>420 nm）Under, be difficult to the organic pollutions such as the rhodamine B degraded, methyl orange and methylene blue with prepared La doped class graphite phase carbon nitride catalysis material degradation biological, with this come prove the material have superior visible light catalytic performance.By cycle down solution methyl orange the experiment proves that the La doped class graphite phase carbon nitride catalysis material of the present invention has good cyclical stability, there is higher actual application value.The material belongs to inorganic catalysis material, and photocatalytic activity under visible light is higher, has good application prospect in the field of environment protection such as treatment of Organic Wastewater and low-carbon energy-saving.
Description
Technical field
The present invention relates to a kind of preparation methods of La doped class graphite phase carbon nitride catalysis material, specific to belong to photocatalysis material
Expect preparation field.
Background technology
In recent years, along with the rapid industrial development in our country, the economic level of the people is greatly improved, but therewith
And the various problem of environmental pollutions come, especially water pollution problems are also gradually caused to the significant damage that people's lives are brought
Society payes attention to, and waste water that is unprocessed or dealing with improperly has produced serious harm to the health of the mankind.Needle
To this problem, there are following several frequently seen processing method, but all existing defects at present.Such as：Chemical method energy expenditure is larger, wave
Take resource；Physical only makes the form of pollutant change, and pollutant remaining processing sequences are complicated；Bioanalysis influence factor
Too much, such as peripheral temperature, pH value of sewage water and aeration quantity etc. all have a great impact to microorganism；High-level oxidation technology is easy
It generates secondary pollution generation and it is more demanding to the equipment and instrument of water process etc., the utilization ratio of reagent is low.So how to drop
Low energy consumption reduces secondary pollution, carries out sewage disposal using clean reproducible energy such as solar energy as far as possible, is solved to future
Certainly problem of environmental pollution has very important significance.
Nano semiconductor photocatalysis technology is known as the optimal depollution of environment technology in the world today.Titanium dioxide in 1972
Water can be decomposed under ultraviolet light by, which being found, is made hydrogen, and Nano semiconductor photocatalysis technology is converted into chemistry in solar energy since then
The gate that energy aspect is applied is opened.It studies after decades of development, Nano semiconductor photocatalysis technology is solving environment dirt
Dye problem especially water pollution problems and the new clean energy resource etc. of exploitation show excellent effect, and rapidly from
Practical application is moved towards in theoretical basic research.Traditional nano-metal-oxide semiconductor such as titanium dioxide and zinc oxide etc. are by section
Scholars have carried out extensive research.But the band gap of traditional nano-titanium dioxide and nano zine oxide is all wider,
Therefore there is response to the ultraviolet light of high-energy, however ultraviolet light but only accounts for 4 percent or so of sunlight, therefore in reality
Sunlight under, the application of traditional nano-metal-oxide semiconductor has received prodigious limitation.
Class graphite phase carbon nitride（g-C3N4）It is a kind of novel non-metal semiconductor materials, because its band gap width is relatively narrow about
For 2.7eV, thus can absorbing wavelength be less than the light of 475nm, there is good response to visible light, to breach conventional semiconductors
If titanium dioxide only has ultraviolet light the defect of response, to the utilization ratio higher of sunlight.In addition class graphite phase carbon nitride
Plurality of advantages is such as：Chemical property is stable, thermal stability is high, of low cost, metallic components and the advantages that deriving from a wealth of sources do not make
It becomes the popular catalysis material of scientists Recent study.In addition, class graphite phase carbon nitride also has excellent photodissociation
The function of aquatic products hydrogen, this advantage make it also be had received widespread attention in new development of clean energy field.
In light-catalyzed reaction, class graphite phase carbon nitride can absorb the energy of sunlight, the electronics in catalyst valence band
It will be excited on conduction band, and leave hole in valence band.Later light induced electron and hole can in aqueous solution molecule or
Person's ions binding generates the living radical with reproducibility or oxidisability, wherein the free radical with oxidisability can will be big
Molecular organic pollutants are degraded to carbon dioxide and water or small organic molecule, to play the role of purifying waste water.
During degradation, photochemical catalyst itself does not change.But individually class graphite phase carbon nitride material is in photocatalytic degradation
When water pollutant, light induced electron and hole caused by excited by visible light are easy to compound again, quantum yield
Relatively low, when causing it to be individually used for photocatalytic degradation water pollutant, degradation efficiency is relatively low.For class graphite phase carbon nitride
The above-mentioned shortcoming of catalysis material, researcher have studied many improved methods, wherein it is critically important it is a kind of be exactly pair
Its doping into row element.
Thulium has abundant energy level and special electronic structure, and unique 4f electron transitions characteristic is not only
Rare earth ion can be made to be doped with ion, but also can make rare earth element in the form of semiconductors coupling with partly lead
The progress of body catalysis material is compound, so as to effectively promote the photocatalytic activity of catalysis material.
The present invention is doped modification with the lanthanum element in rare earth element to class graphite phase carbon nitride nano material, prepares
La doped class graphite phase carbon nitride catalysis material.The forbidden band for being entrained in class graphite phase carbon nitride catalysis material of lanthanum element
In introduce impurity energy level, the energy gap of class graphite phase carbon nitride crystal is reduced, so that class graphite phase carbon nitride pair
The absorption spectrum of sunlight is widened, and is improved to the utilization ratio of sunlight.Meanwhile the introducing of lanthanum element can
Active trap center is formed, light induced electron can be captured so that light induced electron and hole quick separating, and inhibit light induced electron
It is compound with hole, to extend the service life of carrier so that the photocatalytic activity of class graphite phase carbon nitride has obtained very big
Raising.
Invention content
The object of the present invention is to provide a kind of preparation methods of La doped class graphite phase carbon nitride catalysis material, use rare earth
Lanthanum element in element is doped modification to class graphite phase carbon nitride nano material, has prepared the nitridation of La doped class graphite-phase
Carbon catalysis material.Being entrained in the forbidden band of class graphite phase carbon nitride catalysis material for lanthanum element introduces impurity energy level, subtracts
The small energy gap of class graphite phase carbon nitride crystal, so that class graphite phase carbon nitride obtains the absorption spectrum of sunlight
It widens, is improved to the utilization ratio of sunlight.Meanwhile the introducing of lanthanum element can form active trap center, it can
To capture light induced electron so that light induced electron and hole quick separating, and the compound of light induced electron and hole is inhibited, to prolong
The service life of carrier is grown so that the photocatalytic activity of class graphite phase carbon nitride is greatly improved.It can be used for solving
Environment and energy problem.
A kind of preparation method of La doped class graphite phase carbon nitride catalysis material, preparation process are as follows：
Step 1：The preparation of class graphite phase carbon nitride
（1）It weighs 2-8g melamine solids to be put into the ceramic crucible with lid, lid is covered and is put into tubular type heating furnace
In, 550 DEG C are warming up to the heating rate of 5 DEG C/min in air atmosphere and heated 4 hours, obtain flaxen class graphite-phase
Azotized carbon nano material is ground spare later；
Step 2：The preparation of La doped class graphite phase carbon nitride catalysis material
（1）It weighs the class graphite phase carbon nitride nano material prepared in 50mg-2g step 1 and puts it into volume ratio and be
1:In 3 ethylene glycol and the 35-45ml mixed solutions of deionized water, ultrasound 30min is mixed later again after stirring 30min
Uniform mixture；
（2）To（1）In lanthanum nitrate hexahydrate solid and continuing magnetic force be added in the mixture that is uniformly mixed stir 1h, stirring is completed
It is transferred into afterwards in reaction kettle and reacts 12h in 180 DEG C of baking oven；
（3）After reaction is completed to be cooled to room temperature, sediment is centrifuged out, twice of precipitation is washed respectively with deionization and ethyl alcohol
Sediment is positioned in vacuum drying chamber after being dried at 60 DEG C and obtains final product by object later.
Wherein, the liner of the reaction kettle described in step 2 is polytetrafluoroethylene material.
Wherein, the class graphite phase carbon nitride weighed in the quality and step 2 of the lanthanum nitrate hexahydrate being added in step 2 is received
The mass ratio of rice material is 1:6、1:3、2:3、1:1.
It is an advantage of the invention that：
Operating procedure of the present invention is simple, by simple solvent thermal reaction can one-step synthesis, can be completed in common lab.
The La doped class graphite phase carbon nitride catalysis material that the present invention prepares is compared with pure class graphite phase carbon nitride, visible
Light（λ>420 nm）Under, it can be difficult to degrade with degradation biological with prepared La doped class graphite phase carbon nitride catalysis material
The organic pollutions such as rhodamine B, methyl orange and methylene blue, there is stronger photocatalytic activity, it is a variety of harmful to have degradation
The ability of dyestuff, the ability for purifying sewage are greatly improved.In addition this product also has good cyclical stability, leads to
It crosses five methines of cycle degradation orange, catalytic activity under visible light also not weaken significantly, there is very high practical application
Value, has good application prospect in the field of environment protection such as treatment of Organic Wastewater and low-carbon energy-saving.
Description of the drawings
Fig. 1 is to weigh the gadolinium nitrate hexahydrate that the pure class graphite phase carbon nitrides of 50mg and embodiment 1-4 correspondences are added respectively
Product prepared by solid masses is in visible light（λ>420nm）The methyl orange solution of a concentration of 10PPm of the lower degradation 50ml of irradiation
Degradation curve.
Fig. 2 is to weigh the gadolinium nitrate hexahydrate that the pure class graphite phase carbon nitrides of 50mg and the correspondence of embodiment 3 are added respectively to consolidate
Product obtained by weight is in visible light（λ>420nm）Degrade respectively under irradiation a concentration of 10PPm of 50ml rhodamine B and methylene
The degradation curve of base indigo plant solution.
Fig. 3 is to weigh the gadolinium nitrate hexahydrate that the pure class graphite phase carbon nitrides of 50mg and the correspondence of embodiment 3 are added respectively to consolidate
Product obtained by weight is in visible light（λ>420nm）It degrades respectively under irradiation the methylene blue solution of a concentration of 10PPm of 50ml
Degradation curve.
Fig. 4（a）Shape appearance figure for the pure class graphite phase carbon nitride tested with scanning electron microscope (SEM),（b）For embodiment 3
The shape appearance figure of the product of gained.
Fig. 5 is that the gadolinium nitrate hexahydrate solid masses that pure class graphite phase carbon nitride and embodiment 1-4 correspondences are added is made
The XRD test charts of standby product.
Fig. 6 is to weigh the product of 3 gained of 50mg embodiments in visible light（λ>420nm）Five 50ml of the lower cycle degradation of irradiation
The degradation effect comparison diagram of the methyl orange solution of a concentration of 10PPm, degradation time each time is 2 hours.
Specific implementation mode
Below by embodiment 1-4, the invention will be further described.
Embodiment 1
A kind of preparation method of La doped class graphite phase carbon nitride catalysis material, preparation process are as follows：
Step 1：The preparation of class graphite phase carbon nitride.
（1）It weighs 5g melamine solids to be put into the ceramic crucible with lid, lid is covered and is put into tubular type heating
In stove, 550 DEG C are warming up to the heating rate of 5 DEG C/min in air atmosphere and heated 4 hours, obtain flaxen class graphite
Phase carbon nitride nano material is ground spare later.
Step 2：The preparation of La doped class graphite phase carbon nitride catalysis material.
（1）It weighs the class graphite phase carbon nitride nano material prepared in 0.3g step 1 to be put into beaker, be added
10ml ethylene glycol adds 30ml deionized waters, then first stirs 30min ultrasound 30min again, obtains uniformly mixed mixing
Object.
（2）To（1）In be added in the mixture that is uniformly mixed and 0.05g lanthanum nitrate hexahydrates solid and continue to use magnetic agitation
Device stirs 1h.It is 50ml that capacity is transferred into after the completion of stirring, and liner is in the reaction kettle of polytetrafluoroethylene material, in 180
DEG C baking oven in react 12h.
（3）After reaction is completed to be cooled to room temperature, sediment is centrifuged out.It is washed respectively twice with deionization and ethyl alcohol
Sediment is positioned in vacuum drying chamber after being dried in 80 DEG C of temperature and obtains final product by sediment later.
Embodiment 2
A kind of preparation method of La doped class graphite phase carbon nitride catalysis material, preparation process are as follows：
Step 1：The preparation of class graphite phase carbon nitride.
（1）It weighs 4g melamine solids to be put into the ceramic crucible with lid, lid is covered and is put into tubular type heating
In stove, 550 DEG C are warming up to the heating rate of 5 DEG C/min in air atmosphere and heated 4 hours, obtain flaxen class graphite
Phase carbon nitride nano material is ground spare later.
Step 2：The preparation of La doped class graphite phase carbon nitride catalysis material.
（1）It weighs the class graphite phase carbon nitride nano material prepared in 0.9g step 1 to be put into beaker, be added
20ml ethylene glycol adds 60ml deionized waters, then first stirs 30min ultrasound 30min again, obtains uniformly mixed mixing
Object.
（2）To（1）In be added in the mixture that is uniformly mixed and 0.3g lanthanum nitrate hexahydrates solid and continue to use magnetic agitation
Device stirs 1h.It is 100ml that capacity is transferred into after the completion of stirring, and liner is in the reaction kettle of polytetrafluoroethylene material, in 180
DEG C baking oven in react 12h.
（3）After reaction is completed to be cooled to room temperature, sediment is centrifuged out.It is washed respectively twice with deionization and ethyl alcohol
Sediment is positioned in vacuum drying chamber after being dried in 80 DEG C of temperature and obtains final product by sediment later.
Embodiment 3
A kind of preparation method of La doped class graphite phase carbon nitride catalysis material, preparation process are as follows：
Step 1：The preparation of class graphite phase carbon nitride.
（1）It weighs 6g melamine solids to be put into the ceramic crucible with lid, lid is covered and is put into tubular type heating
In stove, 550 DEG C are warming up to the heating rate of 5 DEG C/min in air atmosphere and heated 4 hours, obtain flaxen class graphite
Phase carbon nitride nano material is ground spare later.
Step 2：The preparation of La doped class graphite phase carbon nitride catalysis material.
（1）It weighs the class graphite phase carbon nitride nano material prepared in 0.9g step 1 to be put into beaker, be added
20ml ethylene glycol adds 60ml deionized waters, then first stirs 30min ultrasound 30min again, obtains uniformly mixed mixing
Object.
（2）To（1）In be added in the mixture that is uniformly mixed and 0.6g lanthanum nitrate hexahydrates solid and continue to use magnetic agitation
Device stirs 1h.It is 100ml that capacity is transferred into after the completion of stirring, and liner is in the reaction kettle of polytetrafluoroethylene material, in 180
DEG C baking oven in react 12h.
（3）After reaction is completed to be cooled to room temperature, sediment is centrifuged out.It is washed respectively twice with deionization and ethyl alcohol
Sediment is positioned in vacuum drying chamber after being dried in 80 DEG C of temperature and obtains final product by sediment later.
Embodiment 4
A kind of preparation method of La doped class graphite phase carbon nitride catalysis material, preparation process are as follows：
Step 1：The preparation of class graphite phase carbon nitride.
（1）It weighs 3g melamine solids to be put into the ceramic crucible with lid, lid is covered and is put into tubular type heating
In stove, 550 DEG C are warming up to the heating rate of 5 DEG C/min in air atmosphere and heated 4 hours, obtain flaxen class graphite
Phase carbon nitride nano material is ground spare later.
Step 2：The preparation of La doped class graphite phase carbon nitride catalysis material.
（1）It weighs the class graphite phase carbon nitride nano material prepared in 0.4g step 1 to be put into beaker, be added
10ml ethylene glycol adds 30ml deionized waters, then first stirs 30min ultrasound 30min again, obtains uniformly mixed mixing
Object.
（2）To（1）In be added in the mixture that is uniformly mixed and 0.4g lanthanum nitrate hexahydrates solid and continue to use magnetic agitation
Device stirs 1h.It is 50ml that capacity is transferred into after the completion of stirring, and liner is in the reaction kettle of polytetrafluoroethylene material, in 180
DEG C baking oven in react 12h.
（3）After reaction is completed to be cooled to room temperature, sediment is centrifuged out.It is washed respectively twice with deionization and ethyl alcohol
Sediment is positioned in vacuum drying chamber after being dried in 80 DEG C of temperature and obtains final product by sediment later.
The preparation-obtained product 50mg of embodiment 1-4 are weighed respectively, in visible light（λ>420nm）Irradiation under degrade
The degradation effect of the methyl orange solution of 50ml 10PPm compares, and refers to attached drawing 1.By attached drawing 1 it is found that under the irradiation of visible light,
The quality of the lanthanum nitrate hexahydrate of addition is 2 with the mass ratio of class graphite phase carbon nitride nano material:3（Embodiment 3）When prepare
La doped class graphite phase carbon nitride catalysis material degradable organic pollutant methyl orange ability it is most strong.
Product 50mg made from embodiment 3 is weighed in visible light（λ>420nm）Irradiation under for respectively degradation 50ml it is dense
Degree is that the rhodamine B of 10PPm and methylene blue solution, actual effect refer to attached drawing 2 and Fig. 3 respectively.It can by attached drawing 2 and attached drawing 3
Know, under the irradiation of visible light, the mass ratio of the quality and class graphite phase carbon nitride nano material of the lanthanum nitrate hexahydrate of addition
It is 2:3（Embodiment 3）When the La doped class graphite phase carbon nitride catalysis material for preparing, sieve of a concentration of 10PPm of degradation 50ml
Red bright B solution 120min degradation rates are 98.4%, are 1.2 times of pure class graphite phase carbon nitride nano material；Degradation 50ml concentration
It is 99.9% for the methylene blue solution 120min degradation rates of 10PPm, is the 1.02 of pure class graphite phase carbon nitride nano material
Times.
By the scanning electron microscope (SEM) photograph of product（Attached drawing 4）It can be seen that, with a process for preparing pure class graphite phase carbon nitride
Nano material is sheet or bulk morphologies, there is more serious agglomeration between piece and piece, and the surface of piece or block is more smooth.Lanthanum
Compared with pure class graphite phase carbon nitride, nanometer sheet thickness becomes smaller class graphite phase carbon nitride after doping, surface and pure class stone
Compared to becoming more coarse, agglomeration between layers is reduced black phase carbon nitride.
By the XRD test charts of product（Attached drawing 5）It can clearly be seen that class graphite phase carbon nitride crystal is 13 ° in 2 θ of the angle of diffraction
There are two apparent diffraction maximums with 27 ° or so, the two peaks correspond to class graphite phase carbon nitride respectively（100）Crystal face and
（002）Crystal face, for adulterating the class graphite phase carbon nitride of lanthanum element, in addition to finding that in 2 θ of the angle of diffraction be 13 ° and 27 ° or so appearance
Two class graphite phase carbon nitrides characteristic peak except, 2 θ of the angle of diffraction be 17.7 °, 24.4 °, 30.3 °, 42.9 °, 43.7 °,
46.7 ° there is more apparent diffraction maximum, by being analyzed with jade softwares, it is found that these diffraction maximums correspond to the hydrolysate alkali of lanthanum
Formula lanthanum carbonate（LaCO3OH）（JCPDS 49-0981）Peak, illustrate that lanthanum element is to be present in lanthanum in the form of basic carbonate lanthanum to mix
In miscellaneous class graphite phase carbon nitride nano material, and in building-up process lanthanum nitrate hexahydrate addition increase, class
The characteristic diffraction peak that graphite phase carbon nitride is 13 ° and 27 ° in 2 θ gradually weakens, but the location and shape at peak do not become
Change, illustrate that lanthanum element has been evenly dispersed in the inside of class graphite phase carbon nitride in the form of basic carbonate lanthanum, further illustrates
This method realizes the Effective Doping of lanthanum element.
The product of 3 gained of 50mg embodiments is weighed in visible light（λ>420nm）Irradiation five degradation 50ml concentration of lower cycle
For the degradation effect comparison of the methyl orange solution of 10PPm, attached drawing 6 is referred to.By attached drawing 6 it is found that under the irradiation of visible light, cycle
It degrades after the methyl orange solution five times of 50ml a concentration of 10PPm, the La doped class graphite phase carbon nitride light prepared by the present invention is urged
There is no particularly apparent decreases for the photocatalytic activity of change material, when being recycled to the 5th time, the effect for methyl orange solution of degrading
Rate has still reached 96%, illustrates that this product has higher actual application value in organic wastewater process field.
Claims (3)
1. a kind of preparation method of La doped class graphite phase carbon nitride catalysis material, it is characterized in that：Preparation process is as follows：
Step 1：The preparation of class graphite phase carbon nitride
（1）It weighs 2-8g melamine solids to be put into the ceramic crucible with lid, lid is covered and is put into tubular type heating furnace
In, 550 DEG C are warming up to the heating rate of 5 DEG C/min in air atmosphere and heated 4 hours, obtain flaxen class graphite-phase
Azotized carbon nano material is ground spare later；
Step 2：The preparation of La doped class graphite phase carbon nitride catalysis material
（1）It weighs the class graphite phase carbon nitride nano material prepared in 50mg-2g step 1 and puts it into volume ratio and be
1:In 3 ethylene glycol and the 35-45ml mixed solutions of deionized water, ultrasound 30min is mixed later again after stirring 30min
Uniform mixture；
（2）To（1）In lanthanum nitrate hexahydrate solid and continuing magnetic force be added in the mixture that is uniformly mixed stir 1h, stirring is completed
It is transferred into afterwards in reaction kettle and reacts 12h in 180 DEG C of baking oven；
（3）After reaction is completed to be cooled to room temperature, sediment is centrifuged out, twice of precipitation is washed respectively with deionization and ethyl alcohol
Sediment is positioned in vacuum drying chamber after being dried at 60 DEG C and obtains final product by object later.
2. a kind of preparation method of La doped class graphite phase carbon nitride catalysis material as described in claim 1, it is characterized in that：
The liner of reaction kettle described in step 2 is polytetrafluoroethylene material.
3. a kind of preparation method of La doped class graphite phase carbon nitride catalysis material as described in claim 1, it is characterized in that：
The quality of the class graphite phase carbon nitride nano material weighed in the quality and step 2 of the lanthanum nitrate hexahydrate being added in step 2
Than being 1:6、1:3、2:3、1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810252117.7A CN108607588A (en) | 2018-03-26 | 2018-03-26 | A kind of preparation method of La doped class graphite phase carbon nitride catalysis material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810252117.7A CN108607588A (en) | 2018-03-26 | 2018-03-26 | A kind of preparation method of La doped class graphite phase carbon nitride catalysis material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108607588A true CN108607588A (en) | 2018-10-02 |
Family
ID=63658709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810252117.7A Pending CN108607588A (en) | 2018-03-26 | 2018-03-26 | A kind of preparation method of La doped class graphite phase carbon nitride catalysis material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108607588A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227528A (en) * | 2018-12-18 | 2019-09-13 | 阜阳师范学院 | A kind of Y3+/WO3/g-C3N4B composite photo-catalyst and its preparation and application |
| CN110745794A (en) * | 2019-09-24 | 2020-02-04 | 东北大学 | Preparation method of rare earth metal ion doped graphite phase carbon nitride |
| CN111617806A (en) * | 2020-06-08 | 2020-09-04 | 辽宁大学 | g-C with sodium citrate as matrix3N4MOFs composite photocatalytic material and preparation method and application thereof |
| CN111939964A (en) * | 2020-09-10 | 2020-11-17 | 塔里木大学 | Sm-TiO2Preparation of carbon nitride and application of photocatalytic performance thereof |
| CN112076785A (en) * | 2020-08-28 | 2020-12-15 | 四川大学 | Carbon nitride/lanthanum hydroxide nanofiber membrane and preparation method and application thereof |
| CN112295583A (en) * | 2020-10-23 | 2021-02-02 | 南昌航空大学 | Preparation method and application of zinc sulfide/boronized graphite phase carbon nitride visible-light-induced photocatalyst |
| CN112774708A (en) * | 2019-11-08 | 2021-05-11 | 南京理工大学 | Gd-doped graphite phase carbon nitride-based material and preparation method thereof |
| CN113578369A (en) * | 2021-09-06 | 2021-11-02 | 运城学院 | Modified g-C3N4Material, method for the production thereof and use thereof |
| CN113769779A (en) * | 2021-08-16 | 2021-12-10 | 中化学朗正环保科技有限公司 | Photocatalyst for treating amine-containing organic matter sewage and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707643A (en) * | 2015-02-15 | 2015-06-17 | 南京工程学院 | G-C3N4/La2O3 composite material as well as preparation method and application thereof |
| CN106732711A (en) * | 2016-11-23 | 2017-05-31 | 贵州医科大学 | A kind of carbonitride and cadmium ferrite composite photocatalyst material and preparation method thereof |
-
2018
- 2018-03-26 CN CN201810252117.7A patent/CN108607588A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707643A (en) * | 2015-02-15 | 2015-06-17 | 南京工程学院 | G-C3N4/La2O3 composite material as well as preparation method and application thereof |
| CN106732711A (en) * | 2016-11-23 | 2017-05-31 | 贵州医科大学 | A kind of carbonitride and cadmium ferrite composite photocatalyst material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HANQIANG ZHANG等: "Lanthanum loaded graphitic carbon nitride nanosheets for highly sensitive and selective fluorescent detection of iron ions", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| XINSHAN RONG等: "Synthesis of porous g-C3N4/La and enhanced photocatalytic activity for the degradation of phenol under visible light irradiation", 《JOURNAL OFSOLIDSTATECHEMISTRY》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227528A (en) * | 2018-12-18 | 2019-09-13 | 阜阳师范学院 | A kind of Y3+/WO3/g-C3N4B composite photo-catalyst and its preparation and application |
| CN110745794B (en) * | 2019-09-24 | 2022-06-03 | 东北大学 | Preparation method of rare earth metal ion doped graphite phase carbon nitride |
| CN110745794A (en) * | 2019-09-24 | 2020-02-04 | 东北大学 | Preparation method of rare earth metal ion doped graphite phase carbon nitride |
| CN112774708A (en) * | 2019-11-08 | 2021-05-11 | 南京理工大学 | Gd-doped graphite phase carbon nitride-based material and preparation method thereof |
| CN112774708B (en) * | 2019-11-08 | 2023-01-13 | 南京理工大学 | Gd-doped graphite phase carbon nitride-based material and preparation method thereof |
| CN111617806A (en) * | 2020-06-08 | 2020-09-04 | 辽宁大学 | g-C with sodium citrate as matrix3N4MOFs composite photocatalytic material and preparation method and application thereof |
| CN111617806B (en) * | 2020-06-08 | 2023-08-11 | 辽宁大学 | g-C with sodium citrate as matrix 3 N 4 MOFs composite photocatalytic material and preparation method and application thereof |
| CN112076785A (en) * | 2020-08-28 | 2020-12-15 | 四川大学 | Carbon nitride/lanthanum hydroxide nanofiber membrane and preparation method and application thereof |
| CN112076785B (en) * | 2020-08-28 | 2021-09-14 | 四川大学 | Carbon nitride/lanthanum hydroxide nanofiber membrane and preparation method and application thereof |
| CN111939964A (en) * | 2020-09-10 | 2020-11-17 | 塔里木大学 | Sm-TiO2Preparation of carbon nitride and application of photocatalytic performance thereof |
| CN112295583A (en) * | 2020-10-23 | 2021-02-02 | 南昌航空大学 | Preparation method and application of zinc sulfide/boronized graphite phase carbon nitride visible-light-induced photocatalyst |
| CN113769779A (en) * | 2021-08-16 | 2021-12-10 | 中化学朗正环保科技有限公司 | Photocatalyst for treating amine-containing organic matter sewage and preparation method and application thereof |
| CN113769779B (en) * | 2021-08-16 | 2023-12-29 | 中化学朗正环保科技有限公司 | Photocatalyst for treating sewage containing amine organic matters, and preparation method and application thereof |
| CN113578369A (en) * | 2021-09-06 | 2021-11-02 | 运城学院 | Modified g-C3N4Material, method for the production thereof and use thereof |
| CN113578369B (en) * | 2021-09-06 | 2023-10-27 | 运城学院 | Modified g-C 3 N 4 Material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108607588A (en) | A kind of preparation method of La doped class graphite phase carbon nitride catalysis material | |
| CN106669759B (en) | Phosphorus sulphur codope graphite phase carbon nitride photochemical catalyst and its preparation method and application | |
| CN103480384B (en) | A kind of preparation method of composite bismuth vanadium photocatalyst of strontium ferrite load | |
| CN108772093A (en) | A kind of high visible-light activity graphite phase carbon nitride nanometer sheet and preparation method thereof | |
| CN106517341B (en) | A kind of method and its application for preparing manganese dioxide nano catalyst | |
| CN106669755B (en) | Application in nitrogen Fluorin doped barium titanate photocatalyst and its under visible light degradating organic dye | |
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN108686691A (en) | A kind of preparation method of Gd2 O3 class graphite phase carbon nitride catalysis material | |
| CN110980917B (en) | Method for degrading printing and dyeing wastewater by using graphite-phase carbon nitride activated persulfate under dark reaction condition | |
| CN110465303A (en) | A kind of LaNiO of calcium analysis3The preparation method and application of perovskite type photocatalyst | |
| CN108686665A (en) | A kind of preparation method of nanometer rods zinc ferrite In-situ reaction lamella photocatalysis material of titanium dioxide | |
| CN107824174A (en) | A kind of titanium dioxide quantum dot/carbon ball composite and preparation method thereof | |
| CN110479341A (en) | A kind of hydrogenation modification pucherite/class graphite phase carbon nitride composite photo-catalyst and preparation method thereof | |
| CN108940332A (en) | A kind of high activity MoS2/g-C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst | |
| CN110280289A (en) | A kind of carbonitride catalysis material and preparation method thereof | |
| CN106582722A (en) | Composite photocatalysis system, and preparation method and application thereof | |
| CN114471711B (en) | Polythiophene-carbon nitride composite photocatalyst and preparation method and application thereof | |
| CN102500406B (en) | Iron, nitrogen and fluoride co-doped titanium dioxide (TiO2) photocatalyst and application thereof in degrading organic pollutants in visible light | |
| CN109482238A (en) | A kind of titanous-titanium dioxide-porphyrin/nitridation carbon composite photocatalyst and preparation method thereof | |
| CN109225280A (en) | A kind of tri compound visible light catalyst and its preparation method and application | |
| CN109772423B (en) | Phosphorus and bismuth co-doped porous graphite phase carbon nitride photocatalyst and application thereof | |
| CN112495400A (en) | SnS with S vacancy2Preparation of nanosheet and application thereof in photodegradation of Cr (VI) | |
| CN106957065A (en) | A kind of supper-fast preparation method of N, Ti3+ codope porous TiO2 nanometer sheet | |
| CN110102326A (en) | Modified carbonitride composite photocatalyst material of the supported porous charcoal of a kind of nanogold and the preparation method and application thereof | |
| CN113578368B (en) | g-C 3 N 4 /Ag 3 PO 4 /BiFeO 3 Preparation method and application of composite visible light catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181002 |
|
| RJ01 | Rejection of invention patent application after publication |