CN108246334A - A kind of functionalization tri compound catalysis material and preparation method thereof and purposes - Google Patents
A kind of functionalization tri compound catalysis material and preparation method thereof and purposes Download PDFInfo
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- CN108246334A CN108246334A CN201810089444.5A CN201810089444A CN108246334A CN 108246334 A CN108246334 A CN 108246334A CN 201810089444 A CN201810089444 A CN 201810089444A CN 108246334 A CN108246334 A CN 108246334A
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- functionalization
- catalysis material
- tri compound
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 42
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002351 wastewater Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 13
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 7
- 239000003814 drug Substances 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical class COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000004900 laundering Methods 0.000 claims description 3
- 150000007974 melamines Chemical class 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000013517 stratification Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- 239000011159 matrix material Substances 0.000 claims 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- -1 places 8~12 hours Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of functionalization tri compound catalysis materials and preparation method and application, carbonitride is prepared first, graphene oxide and bismuth ferrite are prepared again, the surface that carbonitride and bismuth ferrite particle are finally combined to graphene oxide prepares functionalization tri compound catalysis material, and the functionalization tri compound catalysis material of preparation is easy to separation of solid and liquid and recycling.Functionalization tri compound catalysis material prepared by the present invention can effectively remove the hexavalent chromium in water, and the pH value and back-ground electolyte of solution can have an impact the removal capacity of functionalization tri compound catalysis material.The present invention can be used for the processing of the chromate waste waters of discharges such as electroplate factory, smeltery, Electronics Factory.
Description
Technical field
The invention belongs to environment functional materials and water process new technical field, and in particular to a kind of functionalization tri compound light
Catalysis material and preparation method thereof and purposes.
Background technology
At present, China's heavy metal pollution problem protrudes.With the rapid development of industry, a large amount of heavy metal contaminants pass through
Various modes are discharged into water body, and the heavy metal pollution of water body is difficult to control, and seriously polluted place or even have been influenced
The safety of agricultural and sideline product.Therefore it is badly in need of the waste water that a kind of efficient and economic technology of searching discharges enterprise to handle.We
Generally wastewater treatment is carried out with the methods of ion exchange, absorption, redox, electro-deposition, filtering, chemical precipitation, infiltration.Closely
Nian Lai, photocatalytic method processing heavy metal wastewater thereby enter the sight of people.Photocatalytic method has normal temperature and pressure, Non-toxic, quick
Efficiently, the advantages that selectivity good, low power consuming, the attention being subject to is growing day by day.Although most of photocatalytic method deoxidization, degradation waste water
Middle heavy metal ion is also in the laboratory research stage, but the research about this respect is more and more.It uses at present
The type and catalytic efficiency of photochemical catalyst are all very limited.Therefore, researching and developing novel has high catalytic amount, high efficiency and cheap
Practical photochemical catalyst becomes a key matter of science and technology of further development and application photocatalytic method.
Graphite phase carbon nitride (g-C3N4) it is polymer semiconductor, there is unique electronic band structure and excellent chemistry
Stability can be used as visible-light photocatalyst, because it is cheap, stabilization, the not characteristics such as metallic components, be widely used in the sun
Can photocatalytic conversion, such as degradation, selective light synthesis and the photodissociation aquatic products hydrogen production oxygen of organic pollution cause that people's is wide
General concern.g-C3N4It is not only cheap to stablize, meet its basic demand as photochemical catalyst, and be also equipped with band structure and easily adjust
The features such as chemical composition of control and polymer semiconductor is the research direction for being worth further investigation.g-C3N4Also there is conduction band electron
The characteristics of reducing power is by force and valence band hole oxidability is weak, g-C3N4Can superoxide radical be generated with activate molecular oxygen
(O2-).Due to g-C3N4Exciton binding energy with photo-generated carrier is high, photo-generate electron-hole is compound seriously, quantum efficiency is low,
Specific surface area is small, energy gap is larger, is unfavorable for the reasons such as the recycling of separation of solid and liquid and catalyst after the completion of catalysis, limits it
It is compound to prevent it from the large-scale promotion application in Practical Project in the application of photocatalysis field.To have magnetic bismuth ferrite
The graphene oxide and g-C strong with conductive capability3N4It is compound, its separating capacity and photo-catalysis capability can be improved.By combined pollutant
For the photo catalytic reduction removal of Cr VI in water, effective technological borrowing can be provided for the processing of heavy metal wastewater thereby.
Invention content
The technical problems to be solved by the invention are：For technical problem of the existing technology, a kind of catalytic is developed
The strong and efficient functionalization tri compound catalysis material available for photocatalysis treatment heavy metal ion of energy.
A kind of preparation method of functionalization tri compound catalysis material proposed by the present invention, is by bismuth ferrite and carbonitride
It is supported on graphene oxide, the functionalization tri compound catalysis material of preparation can realize quick separating simultaneously by externally-applied magnetic field
Increase its redox ability, be as follows：
(1) 20~80g melamines are weighed in crucible, add distilled water that it is made not have a drug, after stratification, outwell upper strata
Clear liquid, then absolute ethyl alcohol is added not have drug, it stands, after its layering, outwells supernatant liquor, crucible is put into Muffle furnace, first not
Lid lid heats 10~60min under the conditions of 40~100 DEG C, then closes the lid, and it is small that 2~6 are heated under the conditions of 400~800 DEG C
When, it is cooled to room temperature and grinds screening, obtain carbonitride；
(2) by graphite powder, K2S2O4And P2O5It is small that the reaction 2~8 at 50~100 DEG C is added in 10~50mL concentrated sulfuric acids
When, the graphite powder, K2S2O4With P2O5Mass ratio be 1：(0.5~2)：(0.5~2), the concentrated sulfuric acid a concentration of 90~
98%, 20~40 DEG C are subsequently cooled to, adds in 800~1200mL ultra-pure waters, places 8~12 hours, product is washed to neutrality
Obtain pre-oxidation graphite after drying at 40~80 DEG C afterwards；
(3) the pre-oxidation graphite that step (2) obtains is added in 200~300mL concentrated sulfuric acids, adds NaNO3With
KMnO4, a concentration of the 90~98% of the concentrated sulfuric acid, the pre-oxidation graphite, NaNO3With KMnO4Mass ratio be 1：(0.5~
2)：(10~50) are reacted 2~6 hours at 0~5 DEG C, are warming up at 30~40 DEG C and are reacted 1~4 hour, and addition 200~
800mL ultra-pure waters, react 1~6 hour under the conditions of 80~100 DEG C, then add in 800~1200mL ultra-pure waters and 20~
60mLH2O2, the H2O2A concentration of 20~30%, the reaction was continued 1~6 hour, by obtained product with a concentration of 5~15%
HCl solution washs, then is washed with massive laundering to neutrality, and ultrasonic disperse obtains graphene oxide in 1~4 hour at 30~60 DEG C
Aqueous suspensions；
(4) ferric nitrate, bismuth nitrate are dissolved in 100~300mL ethylene glycol monomethyl ethers, add in the nitric acid of 0.1~0.5mL,
Citric acid is dissolved in 50~200mL ethylene glycol, the mass ratio of the ferric nitrate, bismuth nitrate and citric acid is 1：(0.5~2)：
(0.1~2), the concentration of nitric acid are 0.01~0.15mol/L, described two solution are mixed, and under the conditions of 40~80 DEG C
Heating stirring 1~4 hour obtains light brown after the solution after heating stirring is heated 6~13 hours under the conditions of 50~150 DEG C
Gel pours into gained gel in crucible, 10~40min is heated under the conditions of 100~320 DEG C, then in 300~800 DEG C of conditions
Lower calcining 1~5 hour, grinds after cooling, obtains bismuth ferrite；
(5) ferrous acid that the carbonitride that obtains step (1), the graphene oxide that step (3) is obtained and step (4) obtain
Bismuth is dissolved in the methanol of 100~400mL, and the mass ratio of the carbonitride, graphene oxide water solution and bismuth ferrite is 1：(20
~50)：(0.5~2), ultrasonic disperse 1~6 hour under the conditions of 30~80 DEG C, in an oven dry 3 under the conditions of 50~100 DEG C
The functionalization tri compound catalysis material is obtained after~8 hours.
The present invention also provides a kind of above-mentioned functionalization tri compound catalysis material be applied to go water removal in heavy metal from
The method of son, the described method comprises the following steps：A certain amount of hexavalent chromium wastewater is taken, the hexavalent chromium concentration of the waste water is
0.001~0.1g/L, it is 1~12 to adjust pH value, and a certain amount of functionalization tri compound catalysis material is added in waste water,
Additive amount in every liter of waste water is calculated as 0.05~3g with functionalization tri compound catalysis material weight, rotating speed for 500~
It is reacted on the magnetic stirring apparatus of 2000rpm 0~8 hour, after some time plus illumination is reacted, and is taken at regular intervals
Sample is primary, identical per sample time interval twice, after the completion of reaction with magnet by functionalization tri compound catalysis material with it is molten
Liquid detaches, and completes the removal to Cr VI in waste water.
Compared with prior art, the advantage of the invention is that：
1. the raw material sources used in the functionalization tri compound catalysis material preparation process of the present invention are extensive, and price
Cheap, primary raw material is common chemical products.
2. product prepared by the method for the present invention is nontoxic, environmentally friendly.
3. the preparation process of the functionalization tri compound catalysis material of the present invention is simple and convenient to operate, it is easy to accomplish work
Industry metaplasia is produced.
4. the functionalization tri compound catalysis material of the present invention is high to the photocatalysis efficiency of heavy metal ion in water, and
Functionalization tri compound catalysis material is easy to that solution detaches with treated, can recycle.For heavy metal in waste water dirt
The improvement of dye and heavy metal resources provide new approach.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram (SEM) of the functionalization tri compound catalysis material of the embodiment of the present invention 1.
Specific embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
Embodiment 1：
A kind of preparation method of functionalization tri compound catalysis material of the present invention：
30g melamines are weighed in crucible, add distilled water that it is made not have a drug, after stratification, outwell supernatant liquor, then
Absolute ethyl alcohol is added not have drug, is stood, after its layering, outwells supernatant liquor, crucible is put into Muffle furnace, first not lid lid,
40min is heated under the conditions of 70 DEG C, then is closed the lid, is heated 3 hours under the conditions of 600 DEG C, is cooled to room temperature and grinds screening,
Obtain carbonitride.
By 6g graphite powders, 5g K2S2O8With 5g P2O5It is added in the concentrated sulfuric acid that 24mL mass concentrations are 98%, at 80 DEG C
Lower reaction 4.5 hours, is subsequently cooled to room temperature, adds in 1000mL ultra-pure waters, places 12 hours, after product is washed to neutrality
Pre-oxidation graphene is dried to obtain at 60 DEG C；Obtained pre-oxidation graphite is added to the dense sulphur that 240mL mass concentrations are 98%
In acid, 5g NaNO are added3With 30g KMnO4, reacted 4 hours at 0 DEG C, be warming up at 35 DEG C and react 2 hours, added in
500mL ultra-pure waters react 1 hour under the conditions of 98 DEG C, then add in 1000mL ultra-pure waters and 40mLH2O2, it is 2 small that the reaction was continued
When, obtained product is washed, then washed with massive laundering to neutrality with a concentration of 10% HCl solution, and ultrasonic at 50 DEG C
Dispersion obtains the graphene oxide aqueous suspensions that mass concentration is 5mg/mL for 2 hours.
32.3192g ferric nitrates, 38.8064g bismuth nitrates are dissolved in 200mL ethylene glycol monomethyl ethers, add in 0.2mL
Citric acid is dissolved in 100mL ethylene glycol by the nitric acid of 0.1mol/L, and described two solution are mixed, and is added under the conditions of 60 DEG C
Thermal agitation 1 hour obtains light brown gel, by gained after the solution after heating stirring is heated 10 hours under the conditions of 100 DEG C
Gel is poured into crucible, 30min is heated under the conditions of 200 DEG C, then calcined 2 hours under the conditions of 500 DEG C, is ground, obtain after cooling
To bismuth ferrite.
Carbonitride 3g, graphene oxide water solution 29mL and the bismuth ferrite 3g obtained is dissolved in the methanol of 100mL,
Ultrasonic disperse 3 hours under the conditions of 50 DEG C obtain the functionalization tri compound light after 6 hours dry under the conditions of 80 DEG C in an oven
Catalysis material.
Functionalization tri compound catalysis material appearance obtained above is brown, places it under scanning electron microscope, knot
Structure is as shown in Figure 1, it can be seen that three kinds of materials can be very good compound.
Embodiment 2：
The functionalization tri compound catalysis material of the present invention includes the following steps for going heavy metal ion in water removal：
The hexavalent chromium wastewater of a concentration of 5mg/L of 200mL is taken, pH value is adjusted with hydrochloric acid or sodium hydroxide in the range of 2~8,
Functionalization tri compound catalysis material made from embodiment 1 is added in wastewater sample, the additive amount in every liter of waste water with
Functionalization tri compound catalysis material weight is calculated as 2.5g, reactor is placed on the magnetic stirring apparatus that rotating speed is 1000rpm
It is reacted, per 20min, sampling is primary, and after 1 hour plus illumination is reacted, and reaction continues 3 hours altogether.Six in sample
The concentration of valency chromium ion is measured using ultraviolet spectrophotometry, and the removal rate of calculating the results are shown in Table 1.
Table 1：PH value removes functionalization trielement composite material the influence of hexavalent chromium in water removal
| PH value | 2 | 4 | 6 | 8 |
| Hexavalent chromium removal rate (%) | 100% | 72.8% | 39.55% | 35.2% |
As shown in Table 1, functionalization trielement composite material reduces the removal amount of hexavalent chromium with the increase of pH value,
When pH value be less than or equal to 2 when removal amount reach balance.
Embodiment 3：
The functionalization tri compound catalysis material of the present invention includes the following steps for going heavy metal ion in water removal：
It is 2 that by functionalization tri compound catalysis material made from embodiment 1, to be respectively added to volume, which be the initial pH of 200mL,
Molar concentration be 0.005mol/L back-ground electolyte be Na2SO4、CaCl2And NaNO3Hexavalent chromium wastewater in, Cr VI from
For the initial concentration of son for 5mg/L, the additive amount in every liter of waste water is calculated as 2.5g with functionalization tri compound catalysis material weight,
Reactor is placed on the magnetic stirring apparatus that rotating speed is 1000rpm and is reacted, sampling is primary (about 5mL) per 20min, 1
After hour plus illumination is reacted, and reaction continues 3 hours altogether.The concentration of hexavalent chromium in sample uses ultraviolet spectrometry light
Degree method is measured, and the removal rate of calculating the results are shown in Table 2.
Table 2：Back-ground electolyte removes functionalization trielement composite material the influence of hexavalent chromium in water removal
| Back-ground electolyte | Nothing | Na2SO4 | CaCl2 | NaNO3 |
| Hexavalent chromium removal rate (%) | 92.35% | 79.3% | 95.25% | 84.35% |
As shown in Table 2, three kinds of back-ground electolytes have the removal amount of hexavalent chromium functionalization trielement composite material
It influences, wherein Na2SO4And NaNO3It can inhibit its removal to Cr VI, and CaCl2It can promote its removal to Cr VI.
The above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment,
With various process programs of the present inventive concept without substantial differences in protection scope of the present invention.
Claims (3)
1. a kind of functionalization tri compound catalysis material, which is characterized in that the functionalization tri compound catalysis material with
Graphene oxide is matrix, and being loaded on matrix has carbonitride and bismuth ferrite particle.
2. a kind of preparation method of functionalization tri compound catalysis material as described in claim 1, includes the following steps：
(1) 20~80g melamines are weighed in crucible, add distilled water that it is made not have a drug, after stratification, it is clear to outwell upper strata
Liquid, then absolute ethyl alcohol is added not have drug, it stands, after its layering, outwells supernatant liquor, crucible is put into Muffle furnace, is not covered first
Lid heats 10~60min under the conditions of 40~100 DEG C, then closes the lid, and it is small that 2~6 are heated under the conditions of 400~800 DEG C
When, it is cooled to room temperature and grinds screening, obtain carbonitride；
(2) by graphite powder, K2S2O4And P2O5It is added in 10~50mL concentrated sulfuric acids and is reacted 2~8 hours at 50~100 DEG C, institute
State graphite powder, K2S2O4With P2O5Mass ratio be 1：(0.5~2)：(0.5~2), a concentration of the 90~98% of the concentrated sulfuric acid,
20~40 DEG C are subsequently cooled to, adds in 800~1200mL ultra-pure waters, is placed 8~12 hours, 40 after product is washed to neutrality
Pre-oxidation graphite is obtained at~80 DEG C after drying；
(3) the pre-oxidation graphite that step (2) obtains is added in 200~300mL concentrated sulfuric acids, adds NaNO3And KMnO4, institute
State a concentration of the 90~98% of the concentrated sulfuric acid, the pre-oxidation graphite, NaNO3With KMnO4Mass ratio be 1：(0.5~2)：(10~
50) it, is reacted 2~6 hours at 0~5 DEG C, is warming up at 30~40 DEG C and reacts 1~4 hour, add in 200~800mL ultra-pure waters,
It is reacted under the conditions of 80~100 DEG C 1~6 hour, then adds in 800~1200mL ultra-pure waters and 20~60mLH2O2, the H2O2
A concentration of 20~30%, the reaction was continued 1~6 hour, and obtained product is washed, then use with a concentration of 5~15% HCl solution
Massive laundering is washed to neutrality, and ultrasonic disperse obtains graphene oxide aqueous suspensions in 1~4 hour at 30~60 DEG C；
(4) ferric nitrate, bismuth nitrate are dissolved in 100~300mL ethylene glycol monomethyl ethers, the nitric acid of 0.1~0.5mL are added in, by lemon
Lemon acid is dissolved in 50~200mL ethylene glycol, and the mass ratio of the ferric nitrate, bismuth nitrate and citric acid is 1：(0.5~2)：(0.1
~2), the concentration of nitric acid is 0.01~0.15mol/L, and described two solution are mixed, and is heated under the conditions of 40~80 DEG C
Stirring 1~4 hour obtains light brown solidifying after the solution after heating stirring is heated 6~13 hours under the conditions of 50~150 DEG C
Glue pours into gained gel in crucible, 10~40min is heated under the conditions of 100~320 DEG C, then under the conditions of 300~800 DEG C
Calcining 1~5 hour, grinds after cooling, obtains bismuth ferrite；
(5) bismuth ferrite that the carbonitride that obtains step (1), the graphene oxide that step (3) is obtained and step (4) obtain is molten
For solution in the methanol of 100~400mL, the mass ratio of the carbonitride, graphene oxide water solution and bismuth ferrite is 1：(20~
50)：(0.5~2), ultrasonic disperse 1~6 hour under the conditions of 30~80 DEG C, in an oven dry 3~8 under the conditions of 50~100 DEG C
The functionalization tri compound catalysis material is obtained after hour.
3. the functionalization tri compound catalysis material described in a kind of claim 2 is applied to go the side of heavy metal ion in water removal
Method the described method comprises the following steps：Take a certain amount of hexavalent chromium wastewater, the hexavalent chromium concentration of the waste water for 0.001~
0.1g/L, it is 1~12 to adjust pH value, and a certain amount of functionalization tri compound catalysis material is added in waste water, and every liter useless
Additive amount in water is calculated as 0.05~3g with functionalization tri compound catalysis material weight, is 500~2000rpm's in rotating speed
It is reacted on magnetic stirring apparatus 0~8 hour, after some time plus illumination is reacted, and sampling is primary at regular intervals, often
Sample time interval is identical twice, is detached functionalization tri compound catalysis material with solution with magnet after the completion of reaction, complete
The removal of Cr VI in pairs of waste water.
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