CN108993399A - It is a kind of with absorption and the difunctional catalyst of photocatalysis and its synthesis and methods for using them - Google Patents
It is a kind of with absorption and the difunctional catalyst of photocatalysis and its synthesis and methods for using them Download PDFInfo
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- absorption
- photocatalysis
- graphene oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 61
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 57
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 52
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- 239000010439 graphite Substances 0.000 claims abstract description 41
- 239000011651 chromium Substances 0.000 claims abstract description 40
- 239000010865 sewage Substances 0.000 claims abstract description 38
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 30
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 18
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen Graphite alkene Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005829 trimerization reaction 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F2101/10—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
It is a kind of with absorption and the difunctional catalyst of photocatalysis and its synthesis and methods for using them, it is related to photochemical catalyst and preparation method and application.It is the single technical problem of catalyst function that solve existing processing heavy metal Cr VI and dyestuff, and catalyst of the invention is combined by cobaltosic oxide, graphite phase carbon nitride and graphene oxide.Preparation method: one, graphene oxide is prepared；Two, graphene oxide dispersion, carbonitride dispersion liquid and N, N-2- methyl pyrrolidone ultrasonic mixing is uniform, acetic acid, CTAB, cobalt nitrate and thiocarbamide are added, it is agitated to obtain precursor liquid；Precursor liquid obtains having absorption and the difunctional catalyst of photocatalysis through hydro-thermal reaction.Using: the pH containing Cr VI and the treatment sewage of methyl blue is adjusted to 2~6, catalyst is then added, is irradiated under natural light or xenon lamp, so that it may complete the processing of sewage.It can be used for the process field of the sewage containing heavy metal chromium and/or dyestuff.
Description
Technical field
The present invention relates to photochemical catalysts and its preparation method and application, belong to sewage treatment field.
Background technique
" water is Source of life ", however in recent years, with the rapid development of industrial or agricultural, dyestuff and a large amount of of chromic salts are used
Through seriously threatening the health of the mankind, caused by environmental problem gradually cause the concern of people.For the dye contained in water
Material and heavy metal, there are many kind methods can be used at present, such as absorption, photocatalysis, ion exchange, UF membrane, but they
Also all come with some shortcomings place, such as: absorption is only shifted target contaminant, ion exchange and UF membrane cost compared with
Height is not suitable for a large amount of processing of industrial sewage.On the contrary, photocatalysis is a kind of novel and environmental protection the new side for handling sewage
Method.However, only just can be carried out under illumination condition with regard to the catalyst that heavy metal Cr VI and dyestuff are handled at present, function
It is single, limit the use scope of material.
Summary of the invention
The present invention is to solve the single technical problem of catalyst function of existing processing heavy metal Cr VI and dyestuff,
And it provides a kind of with absorption and the difunctional catalyst of photocatalysis and its synthesis and methods for using them.
Have absorption and the difunctional catalyst of photocatalysis of the invention is by cobaltosic oxide, graphite phase carbon nitride and oxygen
Graphite alkene is combined, and is denoted as Co3O4-g-C3N4-GO。
The above-mentioned preparation method with absorption and the difunctional catalyst of photocatalysis, sequentially includes the following steps:
One, the preparation of graphene oxide (GO):
Graphite type material (graphite, graphite worm and crystalline flake graphite) is dispersed in the concentrated sulfuric acid that mass percentage concentration is 98%
In, under the conditions of keeping temperature is 10 DEG C below, sodium nitrate is added, and potassium permanganate is added under conditions of magnetic agitation,
Reaction 3~5 hours；It is warming up to 30~35 DEG C after the reaction was completed to be stirred to react 30~60 minutes, distilled water dilution is added, then heat up
It is reacted 10~30 minutes to 70~90 DEG C, then adds water dilution, remain stationary 2~8 minutes, be cooled to 20~30 DEG C, add
Enter H2O2Until color becomes golden yellow, it is then centrifuged for isolating solid formation, solid formation is first used with 5% salt acid elution, again
Ethanol washing is then centrifuged for being freeze-dried, obtains graphene oxide；
Two, Co3O4-g-C3N4- GO preparation:
A, graphene oxide, graphite phase carbon nitride (g-C are weighed3N4) powder, N, N-2- methyl pyrrolidone, acetic acid
(CH3COOH), cetyl trimethylammonium bromide (CTAB), cobalt nitrate and thiocarbamide；Wherein graphene oxide and g-C3N4Powder
Mass ratio is 1:(0.15~0.6)；The quality and N of graphene oxide, the ratio of the volume of N-2- methyl pyrrolidone are 1g:(300
~400) mL；The quality and CH of graphene oxide3The ratio of the volume of COOH is 1g:(40~80) mL；Graphene oxide and CTAB
Mass ratio be 1:(1~2)；The mass ratio of graphene oxide and cobalt nitrate is 1:(10~20)；Graphene oxide and thiocarbamide
Mass ratio is 1:(6~12)；
B, in deionized water by graphene oxide dispersion, graphene oxide dispersion is obtained；
C, in deionized water by graphite phase carbon nitride dispersion, carbonitride dispersion liquid is obtained；
D, cetyl trimethylammonium bromide (CTAB) is added in ionized water, is configured to CTAB solution；
E, graphene oxide dispersion, carbonitride dispersion liquid and N, N-2- methyl pyrrolidone 2~4h of ultrasonic mixing are obtained
To mixed liquor；By CH3COOH, which is added in mixed liquor, stirs 3~5min；It adds CTAB solution and stirs 10~12h；It is eventually adding
Cobalt nitrate and thiocarbamide continue 0.5~1h of stirring, obtain precursor liquid；
F, precursor liquid is added in reaction kettle, be put into temperature be keep 24 in 180~200 DEG C of air dry oven~
28h after being cooled to room temperature, isolates solid formation deionized water and ethanol washing is clean, then be freeze-dried, and obtains having absorption
The difunctional catalyst with photocatalysis.
It advanced optimizes, graphite type material described in step 1 is graphite, graphite worm or crystalline flake graphite；
It advanced optimizes, the body for the concentrated sulfuric acid that the quality of graphite type material and mass percentage concentration are 98% in step 1
Long-pending ratio is 1g:(20~50) mL；
It advanced optimizes, the mass ratio of the quality of graphite type material and sodium nitrate is 1:(0.4~1 in step 1)；
It advanced optimizes, the mass ratio of the quality of graphite type material and potassium permanganate is 1:(3~6 in step 1)；
It advanced optimizes, H in step 12O2Mass fraction be 10%；
It advanced optimizes, the temperature being freeze-dried in step 1 is -50~-40 DEG C, and the time is 12~20 hours；
It advanced optimizes, graphite phase carbon nitride (g-C in step 2 a3N4) the preparation method is as follows: by thiocarbamide and trimerization
Cyanamide is 1:(1~12 in mass ratio) after ground and mixed, it is heated to 500~600 DEG C and is kept for 3~6 hours, regrinding obtains
CN powder；The ratio of the volume for the sodium hydrate aqueous solution for being 3mol/L by the quality and concentration of CN powder is 1g:(12~40) mL
Ratio, CN powder is added in sodium hydrate aqueous solution, is stirred 1~4 hour under the conditions of 70~90 DEG C of temperature, then surpass
It sound decentralized processing 1~3 hour, repeats stirring and ultrasonic disperse is handled 4~5 times, finally washed with ethyl alcohol and deionized water into
Property, it is then centrifuged for isolating solid formation, dry 6~8h at 100~110 DEG C obtains graphite phase carbon nitride (g-C3N4)。
Advanced optimize, in step 2 in b in graphene oxide dispersion graphene oxide concentration be 0.005~
0.1g/mL；
It advanced optimizes, it is 8~10mg/mL that concentration of carbon is nitrogenized in carbonitride dispersion liquid in c in step 2；
It advanced optimizes, the concentration of CTAB solution is 0.005~0.01g/mL in d in step 2；
Above-mentioned has absorption and the application of the difunctional catalyst of photocatalysis, is using with absorption and the double function of photocatalysis
Pollutant Cr VI and methyl blue in the catalyst treatment sewage of energy.Specific method is as follows: will contain Cr VI and methyl
The pH of blue treatment sewage is adjusted to 2~6, has absorption and the double function of photocatalysis by 0.5~1g is added in every 1L processing sewage
The ratio of the catalyst of energy will have absorption and the difunctional catalyst of photocatalysis be added in treatment sewage, in natural light
Or xenon source irradiates 2~3 hours, by absorption and photocatalysis, completes the place of the sewage containing Cr VI and methyl blue
Reason.
Have absorption and the difunctional catalyst of photocatalysis of the invention is to be dispersed in bigger serface graphite oxide
The g-C of alkene3N4And Co3O4Compound, increase g-C3N4And Co3O4With the contact area of target contaminant, photocatalysis is improved
Characteristic, to improve the removal efficiency of target contaminant.Cr VI after catalyst treatment is reduced to the chromium of trivalent, can be recycled
It recycles, dyestuff is degraded, which can also be used repeatedly.Material of the invention can make full use of sunlight,
The substance with oxidation and reduction can be generated under visible light, therefore this there is absorption and be catalyzed difunctional photochemical catalyst
There is apparent oxidative degradation removal ability to heavy metal chromium reducing power with higher and to methyl blue, it is of the invention
Co3O4-g-C3N4- GO catalyst has absorption and catalysis characteristics, has 20%~30% characterization of adsorption to heavy metal Cr VI
With 70%~80% photocatalysis characteristic.Difunctional catalyst of the invention the advantages of there are also good dispersions, work fast.
Of the invention has absorption and the difunctional catalyst preparation process of photocatalysis simple, and preparation cost is low, prepares item
Part is mild.
It can be used for the process field of the sewage containing heavy metal chromium and/or dyestuff.
Detailed description of the invention
Fig. 1 is the stereoscan photograph with absorption and the difunctional catalyst of photocatalysis prepared by embodiment 1；
Fig. 2 is the XRD spectra with absorption and the difunctional catalyst of photocatalysis prepared by embodiment 1；
Fig. 3 is the stereoscan photograph with absorption and the difunctional catalyst of photocatalysis prepared by embodiment 2；
Fig. 4 is the XRD spectra with absorption and the difunctional catalyst of photocatalysis prepared by embodiment 2；
Fig. 5 is the stereoscan photograph with absorption and the difunctional catalyst of photocatalysis prepared by embodiment 3；
Fig. 6 is the XRD spectra with absorption and the difunctional catalyst of photocatalysis prepared by embodiment 3.
Specific embodiment
Below with reference to embodiment, invention is further described in detail, but protection scope of the present invention be not limited to it is described
Content.
Embodiment 1: the preparation method with absorption and the difunctional catalyst of photocatalysis of the present embodiment, according to the following steps
It carries out:
One, the preparation of graphene oxide (GO):
1g graphite worm is dispersed in the concentrated sulfuric acid that 25mL mass percentage concentration is 98%, is transferred to 10 DEG C of ice below
In aqueous mixtures, 0.5g sodium nitrate is added, and 3g potassium permanganate is added under conditions of magnetic agitation, reacts 3~5 hours；Instead
It should be transferred to 35 DEG C of stirred in water bath after the completion to react 30 minutes, the dilution of 45mL distilled water is added, is transferred to 80 DEG C of water-bath
Then middle reaction 10 minutes adds the dilution of 60mL water, remain stationary 2 minutes, remove water-bath, be cooled to 25 DEG C, quality is added
The H that score is 10%2O2Until color becomes golden yellow, it is then centrifuged for isolating solid formation, solid formation first uses 5% salt
Acid elution is used ethanol washing 2 times three times, again, is then freeze-dried 14 hours under conditions of -50 DEG C, is obtained graphene oxide；
Two, Co3O4-g-C3N4- GO preparation:
A, the g-C of 0.05g graphene oxide, 8mg are weighed3N4Powder, 15mL N, N-2- methyl pyrrolidone, 2mL
CH3CTAB, 0.5g cobalt nitrate and 0.3g thiocarbamide of COOH, 0.05g；Wherein graphene oxide and g-C3N4The mass ratio of powder is
1:(0.15~0.6)；
B, graphene oxide is dispersed in the graphene oxide dispersion for obtaining that concentration is 0.005g/mL in 10mL deionized water
Liquid；
C, graphite phase carbon nitride is dispersed in the deionized water of 10mL, obtains the carbonitride that concentration is 8mg/mL and disperses
Liquid；
D, CTAB is added to the CTAB solution for being configured to that concentration is 0.005g/mL in 10mL water；
E, graphene oxide dispersion, carbonitride dispersion liquid and N, N-2- methyl pyrrolidone ultrasonic mixing 2h are obtained
Brown solution；By CH3COOH is added in mixed liquor and stirs 3min；Add CTAB solution magnetic agitation 10h at room temperature；Finally plus
Enter cobalt nitrate and thiocarbamide continues to stir 0.5h, obtains precursor liquid；
F, precursor liquid is added in reaction kettle, is put into the air dry oven that temperature is 180 DEG C and keeps for 24 hours, being cooled to
It after room temperature, isolates solid formation deionized water and ethyl alcohol and respectively washs 3 times, then be freeze-dried, obtain that there is absorption and photocatalysis
Difunctional catalyst.
Wherein g-C described in step 23N4Powder is prepared with the following method: by 0.5g thiocarbamide and 2g melamine
After amine ground and mixed, it is heated to 500 DEG C and is kept for 3 hours, regrind into powder, obtain CN powder；2g CN powder is added to
50mL concentration is to stir 1 hour under the conditions of 70 DEG C of temperature in 3mol/L sodium hydrate aqueous solution, re-ultrasonic dispersion processing 1
Hour, it repeats stirring and ultrasonic disperse is handled 4 times, finally washed with ethyl alcohol and deionized water to neutrality, be then centrifuged for isolating
Solid formation, dry 6h, obtains graphite phase carbon nitride (g-C at 100 DEG C3N4)。
It is manufactured in the present embodiment have absorption and the difunctional catalyst of photocatalysis stereoscan photograph as shown in Figure 1,
It will be seen from figure 1 that cobaltosic oxide particle is preferable in the dispersibility of surface of graphene oxide, but its granular size is inhomogenous,
It is irregular；
It is manufactured in the present embodiment that there is the XRD spectra of absorption and the difunctional catalyst of photocatalysis as shown in Fig. 2, from Fig. 2
As can be seen that carbonitride crystalline form does not change after processing, the peak of cobaltosic oxide is not sharp.
Have absorption and the difunctional catalyst of photocatalysis to containing Cr VI and methyl blue using manufactured in the present embodiment
Sewage is handled, and specific method is as follows: the concentration of Cr VI is 20mg/L in sewage to be processed, the concentration of methyl blue is
20mg/L；Sewage of the 20mL by processing is taken, its pH value is adjusted to 6, it is manufactured in the present embodiment with absorption and light that 10mg is added
It is catalyzed difunctional catalyst, after placing 30min under dark condition, being transferred to light source is prolonged exposure under the conditions of 100W xenon lamp
150min measures 2mL sewage every 30min respectively and is centrifuged during processing, then molten with UV spectrophotometer measuring
The concentration of Cr VI and methyl blue is remained in liquid.Calculating is learnt, after placement processing under dark condition, Cr VI and methyl blue
Removal rate be respectively 25% and 18%, after 150min treatment with irradiation, the removal rate of Cr VI and methyl blue reaches respectively
To 82% and 79%.
In addition the processing test being made in parallel under natural light, method particularly includes: the concentration of Cr VI in sewage to be processed
Concentration for 20mg/L, methyl blue is 20mg/L；Sewage of the 20mL by processing is taken, its pH value is adjusted to 6, this reality of 10mg is added
That applies example preparation has absorption and the difunctional catalyst of photocatalysis, after placing 30min under dark condition, is transferred to natural light
Lower placement 150min measures 2mL sewage every 30min respectively and is centrifuged, then in UV spectrophotometer measuring solution
Remain the concentration of Cr VI and methyl blue.Calculating is learnt, after placement processing under dark condition, using 150min natural light
After treatment with irradiation, the removal rate of Cr VI and methyl blue respectively reaches 80% and 76%.
Embodiment 2: the preparation method with absorption and the difunctional catalyst of photocatalysis of the present embodiment, according to the following steps
It carries out:
One, the preparation of graphene oxide (GO):
It is below in 98% concentrated sulfuric acid, to be transferred to 10 DEG C that 1.5g crystalline flake graphite is dispersed in 30mL mass percentage concentration
In mixture of ice and water, 0.7g sodium nitrate is added, and 5g potassium permanganate is added under conditions of magnetic agitation, reacts 4 hours；Reaction
It is transferred to 35 DEG C of stirred in water bath after the completion to react 45 minutes, the dilution of 50mL distilled water is added, is transferred in 80 DEG C of water-bath
Then reaction 20 minutes adds the dilution of 75mL water, remain stationary 4 minutes, remove water-bath, be cooled to 25 DEG C, quality point is added
The H that number is 10%2O2Until color becomes golden yellow, it is then centrifuged for isolating solid formation, solid formation first uses 5% hydrochloric acid
It washs 3 times, use ethanol washing 2 times again, be then freeze-dried 14 hours under conditions of -50 DEG C, obtain graphene oxide；
Two, Co3O4-g-C3N4- GO preparation:
A, the g-C of 0.075g graphene oxide, 13.5mg are weighed3N4Powder, 17mL N, N-2- methyl pyrrolidone, 3mL
CH3CTAB, 0.75g cobalt nitrate and 0.4g thiocarbamide of COOH, 0.07g；
B, graphene oxide is dispersed in the graphene oxide dispersion for obtaining that concentration is 0.005g/mL in 12mL deionized water
Liquid；
C, graphite phase carbon nitride is dispersed in the deionized water of 1.5mL, obtains the carbonitride that concentration is 9mg/mL and disperses
Liquid；
D, CTAB is added to the CTAB solution for being configured to that concentration is 0.005g/mL in 12mL water；
E, graphene oxide dispersion, carbonitride dispersion liquid and N, N-2- methyl pyrrolidone ultrasonic mixing 3h are obtained
Brown solution；By CH3COOH is added in mixed liquor and stirs 4min；Add CTAB solution magnetic agitation 11h at room temperature；Finally plus
Enter cobalt nitrate and thiocarbamide continues to stir 45min, obtains precursor liquid；
F, precursor liquid is added in reaction kettle, is put into the furnace that temperature is 190 DEG C and keeps for 24 hours, after being cooled to room temperature, point
It separates out solid formation deionized water and ethyl alcohol respectively to wash 3 times, then is freeze-dried, obtain that there is absorption and photocatalysis is difunctional urges
Agent.
Wherein g-C described in step 23N4Powder is prepared with the following method: by 1.5g thiocarbamide and 4g melamine
After amine ground and mixed, it is heated to 550 DEG C and is kept for 4 hours, regrind into powder, obtain CN powder；3g CN powder is added to
60mL concentration is to stir 2 hours under the conditions of 80 DEG C of temperature in 3mol/L sodium hydrate aqueous solution, re-ultrasonic dispersion processing 2
Hour, it repeats stirring and ultrasonic disperse is handled 4 times, finally washed with ethyl alcohol and deionized water to neutrality, be then centrifuged for isolating
Solid formation, dry 7h, obtains graphite phase carbon nitride (g-C at 105 DEG C3N4)。
It is manufactured in the present embodiment have absorption and the difunctional catalyst of photocatalysis stereoscan photograph as shown in figure 3,
From figure 3, it can be seen that cobaltosic oxide is distributed more uniform on graphene oxide, and granular size is regular compared with embodiment 1；
It is manufactured in the present embodiment that there is the XRD spectra of absorption and the difunctional catalyst of photocatalysis as shown in figure 4, from Fig. 4
As can be seen that cobaltosic oxide crystallinity tends to improve with the increase of various raw materials, peak type is sharp compared with embodiment 1.
Have absorption and the difunctional catalyst of photocatalysis to containing Cr VI and methyl blue using manufactured in the present embodiment
Sewage is handled, and specific method is as follows: the concentration of Cr VI is 20mg/L in sewage to be processed, the concentration of methyl blue is
20mg/L；Sewage of the 20mL by processing is taken, its pH value is adjusted to 4, it is manufactured in the present embodiment with absorption and light that 15mg is added
It is catalyzed difunctional catalyst, after placing 30min under dark condition, being transferred to light source is prolonged exposure under the conditions of 100W xenon lamp
150min measures 2mL sewage every 30min respectively and is centrifuged during this period, then uses UV spectrophotometer measuring solution
The concentration of middle residual Cr VI and methyl blue.Calculating learns, after placement processing under dark condition, Cr VI and methyl blue
Removal rate is respectively 28% and 21%, and after 150min treatment with irradiation, the removal rate of Cr VI and methyl blue is respectively
91% and 86%.
In addition the processing test being made in parallel under natural light, method particularly includes: the concentration of Cr VI in sewage to be processed
Concentration for 20mg/L, methyl blue is 20mg/L；Sewage of the 20mL by processing is taken, its pH value is adjusted to 4, this reality of 15mg is added
That applies example preparation has absorption and the difunctional catalyst of photocatalysis, after placing 30min under dark condition, is transferred to natural light
Lower placement 150min measures 2mL sewage every 30min respectively and is centrifuged, then in UV spectrophotometer measuring solution
Remain the concentration of Cr VI and methyl blue.Calculating is learnt, after placement processing under dark condition, using 150min natural light
After treatment with irradiation, the removal rate of Cr VI and methyl blue respectively reaches 89% and 84%.
Embodiment 3: the preparation method with absorption and the difunctional catalyst of photocatalysis of the present embodiment, according to the following steps
It carries out:
One, the preparation of graphene oxide (GO):
By the graphite powder of 2g200 mesh be dispersed in 50mL mass percentage concentration be 98% the concentrated sulfuric acid in, be transferred to 10 DEG C with
Under mixture of ice and water in, be added 1g sodium nitrate, and under conditions of magnetic agitation be added 6g potassium permanganate, react 5 hours；Instead
It should be transferred to 35 DEG C of stirred in water bath after the completion to react 60 minutes, the dilution of 60mL distilled water is added, is transferred to 90 DEG C of water-bath
Then middle reaction 30 minutes adds the dilution of 90mL water, remain stationary 8 minutes, remove water-bath, be cooled to 25 DEG C, quality is added
The H that score is 10%2O2Until color becomes golden yellow, it is then centrifuged for isolating solid formation, solid formation first uses 5% salt
Acid elution 3 times is used ethanol washing 2 times again, is then freeze-dried 14 hours under conditions of -50 DEG C, is obtained graphene oxide；
Two, Co3O4-g-C3N4- GO preparation:
A, the g-C of 1g graphene oxide, 20mg are weighed3N4Powder, 20mL N, N-2- methyl pyrrolidone, 4mL
CH3CTAB, 1g cobalt nitrate and 0.6g thiocarbamide of COOH, 0.1g；
B, graphene oxide is dispersed in the graphene oxide dispersion for obtaining that concentration is 0.067g/mL in 15mL deionized water
Liquid；
C, graphite phase carbon nitride is dispersed in the deionized water of 2mL, obtains the carbonitride that concentration is 10mg/mL and disperses
Liquid；
D, CTAB is added to the CTAB solution for being configured to that concentration is 0.005g/mL in 15mL water；
E, graphene oxide dispersion, carbonitride dispersion liquid and N, N-2- methyl pyrrolidone ultrasonic mixing 4h are obtained
Brown solution；By CH3COOH is added in mixed liquor and stirs 5min；Add CTAB solution magnetic agitation 12h at room temperature；Finally plus
Enter cobalt nitrate and thiocarbamide continues to stir 60min, obtains precursor liquid；
F, precursor liquid is added in reaction kettle, is put into the furnace that temperature is 200 DEG C and keeps for 24 hours, after being cooled to room temperature, point
It separates out solid formation deionized water and ethyl alcohol respectively to wash 3 times, then is freeze-dried, obtain that there is absorption and photocatalysis is difunctional urges
Agent.
Wherein g-C described in step 23N4Powder is prepared with the following method: by 2g thiocarbamide and 6g melamine
After ground and mixed, it is heated to 600 DEG C and is kept for 6 hours, regrind into powder, obtain CN powder；4g CN powder is added to
80mL concentration is to stir 3 hours under the conditions of 90 DEG C of temperature in 3mol/L sodium hydrate aqueous solution, re-ultrasonic dispersion processing 2
Hour, it repeats stirring and ultrasonic disperse is handled 4 times, finally washed with ethyl alcohol and deionized water to neutrality, be then centrifuged for isolating
Solid formation, dry 7h, obtains graphite phase carbon nitride (g-C at 105 DEG C3N4)。
It is manufactured in the present embodiment have absorption and the difunctional catalyst of photocatalysis stereoscan photograph as shown in figure 5,
From fig. 6, it can be seen that cobaltosic oxide still keeps preferable dispersibility when graphene oxide additional amount is original 2 times, and
Particle is more uniform, regular.
It is manufactured in the present embodiment that there is the XRD spectra of absorption and the difunctional catalyst of photocatalysis as shown in fig. 6, from Fig. 6
As can be seen that showing in conjunction with Fig. 5, when additive amount changes, and the crystal form of original substance in material is had not been changed, only change particle
Pattern.
Have absorption and the difunctional catalyst of photocatalysis to containing Cr VI and methyl blue using manufactured in the present embodiment
Sewage is handled, and specific method is as follows: the concentration of Cr VI is 20mg/L in sewage to be processed, the concentration of methyl blue is
20mg/L；Sewage of the 20mL by processing is taken, its pH value is adjusted to 2, it is manufactured in the present embodiment with absorption and light that 20mg is added
It is catalyzed difunctional catalyst, after placing 30min under dark condition, being transferred to light source is prolonged exposure under the conditions of 100W xenon lamp
150min measures 2mL sewage every 30min respectively and is centrifuged during this period, then uses UV spectrophotometer measuring solution
The concentration of middle residual Cr VI and methyl blue.Calculating learns, after placement processing under dark condition, Cr VI and methyl blue
Removal rate is respectively 30% and 24%, after 150min treatment with irradiation, after 150min treatment with irradiation, and Cr VI and first
The removal rate of base indigo plant is respectively 100% and 95%.
In addition the processing test being made in parallel under natural light, method particularly includes: the concentration of Cr VI in sewage to be processed
Concentration for 20mg/L, methyl blue is 20mg/L；Sewage of the 20mL by processing is taken, its pH value is adjusted to 4, this reality of 15mg is added
That applies example preparation has absorption and the difunctional catalyst of photocatalysis, after placing 30min under dark condition, is transferred to natural light
Lower placement 150min measures 2mL sewage every 30min respectively and is centrifuged, then in UV spectrophotometer measuring solution
Remain the concentration of Cr VI and methyl blue.Calculating is learnt, after placement processing under dark condition, using 150min natural light
After treatment with irradiation, the removal rate of Cr VI and methyl blue respectively reaches 96% and 89%.
Claims (10)
1. a kind of with absorption and the difunctional catalyst of photocatalysis, it is characterised in that the catalyst is by cobaltosic oxide, stone
Black phase carbon nitride and graphene oxide are combined.
2. preparing a kind of method with absorption and the difunctional catalyst of photocatalysis described in claim 1, it is characterised in that
This method sequentially includes the following steps:
One, the preparation of graphene oxide:
Graphite type material is dispersed in the concentrated sulfuric acid that mass percentage concentration is 98%, temperature is being kept to be 10 DEG C of conditions below
Under, sodium nitrate is added, and potassium permanganate is added under conditions of magnetic agitation, reacts 3~5 hours；It is warming up to after the reaction was completed
30~35 DEG C are stirred to react 30~60 minutes, and distilled water dilution is added, then are warming up to 70~90 DEG C of reactions 10~30 minutes, then
Water dilution is added, is remain stationary 2~8 minutes, is cooled to 20~30 DEG C, H is added2O2Until color becomes golden yellow, so
After be centrifugated out solid formation, solid formation first uses 5% salt acid elution, again with ethanol washing, is then centrifuged for being freeze-dried, obtain
Graphene oxide；
Two, Co3O4-g-C3N4- GO preparation:
A, graphene oxide, graphite phase carbon nitride powder, N, N-2- methyl pyrrolidone, acetic acid, cetyl trimethyl are weighed
Ammonium bromide, cobalt nitrate and thiocarbamide；Wherein graphene oxide and g-C3N4The mass ratio of powder is 1:(0.15~0.6)；Graphite oxide
The quality and N of alkene, the ratio of the volume of N-2- methyl pyrrolidone are 1g:(300~400) mL；The quality of graphene oxide with
CH3The ratio of the volume of COOH is 1g:(40~80) mL；The mass ratio of graphene oxide and CTAB are 1:(1~2)；Graphite oxide
The mass ratio of alkene and cobalt nitrate is 1:(10~20)；The mass ratio of graphene oxide and thiocarbamide is 1:(6~12)；
B, in deionized water by graphene oxide dispersion, graphene oxide dispersion is obtained；
C, in deionized water by graphite phase carbon nitride dispersion, carbonitride dispersion liquid is obtained；
D, cetyl trimethylammonium bromide (CTAB) is added in ionized water, is configured to CTAB solution；
E, graphene oxide dispersion, carbonitride dispersion liquid and N, N-2- methyl pyrrolidone 2~4h of ultrasonic mixing are mixed
Close liquid；By CH3COOH, which is added in mixed liquor, stirs 3~5min；It adds CTAB solution and stirs 10~12h；It is eventually adding nitric acid
Cobalt and thiocarbamide continue 0.5~1h of stirring, obtain precursor liquid；
F, precursor liquid is added in reaction kettle, is put into the air dry oven that temperature is 180~200 DEG C and keeps 24~28h, it is cold
But it to after room temperature, isolates solid formation deionized water and ethanol washing is clean, then be freeze-dried, obtain that there is absorption and light to urge
Change difunctional catalyst.
3. a kind of preparation method with absorption and the difunctional catalyst of photocatalysis according to claim 2, feature
It is that graphite type material described in step 1 is graphite, graphite worm or crystalline flake graphite.
4. a kind of preparation method with absorption and the difunctional catalyst of photocatalysis according to claim 2 or 3, special
Sign is that the ratio of the volume for the concentrated sulfuric acid that the quality of graphite type material and mass percentage concentration are 98% in step 1 is 1g:(20
~50) mL.
5. a kind of preparation method with absorption and the difunctional catalyst of photocatalysis according to claim 2 or 3, special
Sign is in step 1 that the mass ratio of the quality of graphite type material and sodium nitrate is 1:(0.4~1).
6. a kind of preparation method with absorption and the difunctional catalyst of photocatalysis according to claim 2 or 3, special
Sign is in step 1 that the mass ratio of the quality of graphite type material and potassium permanganate is 1:(3~6).
7. a kind of preparation method with absorption and the difunctional catalyst of photocatalysis according to claim 2 or 3, special
Sign be graphite phase carbon nitride in step 2 a the preparation method is as follows: being in mass ratio 1:(1~12 by thiocarbamide and melamine)
It after ground and mixed, is heated to 500~600 DEG C and is kept for 3~6 hours, regrinding obtains CN powder；By CN powder quality with
The ratio of the volume for the sodium hydrate aqueous solution that concentration is 3mol/L is 1g:(12~40) ratio of mL, CN powder is added to hydrogen
It in aqueous solution of sodium oxide, is stirred 1~4 hour under the conditions of 70~90 DEG C of temperature, re-ultrasonic dispersion is handled 1~3 hour, is repeated
Stirring and ultrasonic disperse are handled 4~5 times, are finally washed with ethyl alcohol and deionized water to neutrality, are then centrifuged for isolating solid formation,
Dry 6~8h, obtains graphite phase carbon nitride (g-C at 100~110 DEG C3N4)。
8. a kind of preparation method with absorption and the difunctional catalyst of photocatalysis according to claim 2 or 3, special
Sign is in step 2 in b in graphene oxide dispersion that graphene oxide concentration is 0.005~0.1g/mL.
9. a kind of preparation method with absorption and the difunctional catalyst of photocatalysis according to claim 2 or 3, special
Sign is in step 2 in c that it is 8~10mg/mL that concentration of carbon is nitrogenized in carbonitride dispersion liquid.
10. having absorption and the application of the difunctional catalyst of photocatalysis described in claim 1, it is characterised in that the application
It is using with the pollutant Cr VI and methyl blue in absorption and the difunctional catalyst treatment sewage of photocatalysis；Specific side
Method is as follows: the pH containing Cr VI and the treatment sewage of methyl blue being adjusted to 2~6, handles in sewage by every 1L and is added 0.5
~1g has the ratio of absorption and the difunctional catalyst of photocatalysis, will be added with the difunctional catalyst of absorption and photocatalysis
It into treatment sewage, is irradiated 2~3 hours in natural light or xenon source, by absorption and photocatalysis, completion contains six
The processing of the sewage of valence chromium and methyl blue.
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| CN109607525A (en) * | 2019-01-15 | 2019-04-12 | 哈尔滨工业大学 | A kind of preparation method and application for the graphene oxide composite material that fold is mercapto-functionalized |
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| CN111760555A (en) * | 2020-06-08 | 2020-10-13 | 天津科技大学 | Preparation method and application of ZIF-based low-temperature adsorption material |
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| CN111841597A (en) * | 2020-06-22 | 2020-10-30 | 江苏中江材料技术研究院有限公司 | Composite photocatalytic material of cobalt-loaded nitrogen-doped graphene oxide/mesoporous thin-layer carbon nitride and preparation method thereof |
| CN113045976A (en) * | 2021-03-16 | 2021-06-29 | 广东绿色大地化工有限公司 | Nano ceramic anticorrosive water-based paint |
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