CN108993399B - Catalyst with dual functions of adsorption and photocatalysis and synthesis and application methods thereof - Google Patents
Catalyst with dual functions of adsorption and photocatalysis and synthesis and application methods thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 61
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 60
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000009977 dual effect Effects 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title abstract description 4
- 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 77
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 56
- 239000010865 sewage Substances 0.000 claims abstract description 43
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 39
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 36
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 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 32
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 29
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- 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 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 239000007790 solid phase Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007770 graphite material Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 125000000896 monocarboxylic acid group Chemical group 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
- 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
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000005457 ice water Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
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- 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
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—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
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
A catalyst with dual functions of adsorption and photocatalysis and a synthesis and application method thereof relate to a photocatalyst and a preparation method and application thereof. The catalyst is prepared by compounding cobaltosic oxide, graphite phase carbon nitride and graphene oxide. The preparation method comprises the following steps: firstly, preparing graphene oxide; secondly, ultrasonically and uniformly mixing the graphene oxide dispersion liquid, the carbon nitride dispersion liquid and the N, N-2-methyl pyrrolidone, adding acetic acid, CTAB, cobalt nitrate and thiourea, and stirring to obtain a precursor liquid; the precursor solution is subjected to hydrothermal reaction to obtain the catalyst with dual functions of adsorption and photocatalysis. The application comprises the following steps: adjusting the pH value of the sewage to be treated containing hexavalent chromium and methyl blue to 2-6, adding a catalyst, and irradiating under natural light or a xenon lamp to complete the treatment of the sewage. Can be used in the field of treatment of sewage containing heavy metal chromium and/or dye.
Description
Technical Field
The invention relates to a photocatalyst and a preparation method and application thereof, belonging to the field of sewage treatment.
Background
"Water is the source of life", however, in recent years, with the rapid development of industry and agriculture, the use of dye and chromium salt in large quantities seriously threatens human health, and the environmental problems caused by the dye and chromium salt are gradually attracting people's attention. For dyes and heavy metals contained in water, a variety of methods such as adsorption, photocatalysis, ion exchange, membrane separation and the like are available, but all of them have some disadvantages, such as: the adsorption only transfers the target pollutant, and the ion exchange and the membrane separation have high cost and are not suitable for the large-scale treatment of industrial sewage. In contrast, photocatalysis is a novel and environmentally friendly method of treating wastewater. However, the existing catalyst for treating the heavy metal hexavalent chromium and the dye can be carried out only under the condition of illumination, and the function is single, so that the application range of the material is limited.
Disclosure of Invention
The invention aims to solve the technical problem that the existing catalyst for treating heavy metal hexavalent chromium and dye has single function, and provides a catalyst with double functions of adsorption and photocatalysis, and a synthesis and application method thereof.
The catalyst with the double functions of adsorption and photocatalysis is compounded by cobaltosic oxide, graphite phase carbon nitride and graphene oxide, and is marked as Co3O4-g-C3N4-GO。
The preparation method of the catalyst with the adsorption and photocatalysis functions comprises the following steps:
firstly, preparing Graphene Oxide (GO):
dispersing graphite materials (graphite, graphite worms and flake graphite) in concentrated sulfuric acid with the mass percentage concentration of 98%, adding sodium nitrate under the condition of keeping the temperature below 10 ℃, adding potassium permanganate under the condition of magnetic stirring, and reacting for 3-5 hours; after the reaction is finished, heating to 30-35 ℃, stirring for reaction for 30-60 minutes, adding distilled water for dilution, heating to 70-90 ℃, reacting for 10-30 minutes, then adding water for dilution, keeping static for 2-8 minutes, cooling to 20-30 ℃, adding H2O2Until the color becomes golden yellow, centrifugally separating out a solid phase, washing the solid phase with 5% hydrochloric acid, then washing with ethanol, and centrifugally freeze-drying to obtain graphene oxide;
two, Co3O4-g-C3N4-GO preparation:
a. weighing machineGraphene oxide, graphite phase carbon nitride (g-C)3N4) Powder, N-2-methylpyrrolidone, and acetic acid (CH)3COOH), cetyltrimethylammonium bromide (CTAB), cobalt nitrate and thiourea; wherein the graphene oxide is mixed with g-C3N4The mass ratio of the powder is 1: (0.15 to 0.6); the ratio of the mass of graphene oxide to the volume of N, N-2-methylpyrrolidone was 1 g: (300-400) mL; mass of graphene oxide and CH3Volume ratio of COOH 1 g: (40-80) mL; the mass ratio of the graphene oxide to CTAB is 1: (1-2); the mass ratio of the graphene oxide to the cobalt nitrate is 1: (10-20); the mass ratio of the graphene oxide to the thiourea is 1: (6-12);
b. dispersing graphene oxide in deionized water to obtain a graphene oxide dispersion liquid;
c. dispersing graphite-phase carbon nitride in deionized water to obtain carbon nitride dispersion liquid;
d. adding Cetyl Trimethyl Ammonium Bromide (CTAB) into ionized water to prepare a CTAB solution;
e. ultrasonically mixing the graphene oxide dispersion liquid, the carbon nitride dispersion liquid and N, N-2-methyl pyrrolidone for 2-4 hours to obtain a mixed liquid; will CH3Adding COOH into the mixed solution and stirring for 3-5 min; adding a CTAB solution and stirring for 10-12 h; finally, adding cobalt nitrate and thiourea, and continuously stirring for 0.5-1 h to obtain a precursor solution;
f. and adding the precursor solution into a reaction kettle, placing the reaction kettle into a forced air drying oven at the temperature of 180-200 ℃ for 24-28 h, cooling to room temperature, separating out solid phase substances, washing with deionized water and ethanol, and freeze-drying to obtain the catalyst with the adsorption and photocatalysis functions.
Preferably, the graphite material in the step one is graphite, graphite worms or flake graphite;
further optimally, the ratio of the mass of the graphite material to the volume of concentrated sulfuric acid with the mass percentage concentration of 98% in the step one is 1 g: (20-50) mL;
further optimally, the mass ratio of the graphite material to the sodium nitrate in the first step is 1: (0.4 to 1);
and (3) further optimizing, wherein the mass ratio of the graphite material to the potassium permanganate in the step one is 1: (3-6);
further optimized, step one, H2O2The mass fraction of (A) is 10%;
further optimally, the temperature of freeze drying in the step one is-50 to-40 ℃, and the time is 12 to 20 hours;
further preferably, the graphite phase carbon nitride (g-C) in step two3N4) The preparation method comprises the following steps: thiourea and melamine are mixed according to the mass ratio of 1: (1-12) grinding and mixing, heating to 500-600 ℃, keeping for 3-6 hours, and grinding again to obtain CN powder; according to the proportion of the mass of CN powder to the volume of 3mol/L sodium hydroxide aqueous solution of 1 g: (12-40) mL, adding CN powder into a sodium hydroxide aqueous solution, stirring for 1-4 hours at the temperature of 70-90 ℃, performing ultrasonic dispersion treatment for 1-3 hours, repeating stirring and ultrasonic dispersion treatment for 4-5 times, washing with ethanol and deionized water to be neutral, centrifuging to separate out a solid phase, and drying at the temperature of 100-110 ℃ for 6-8 hours to obtain graphite-phase carbon nitride (g-C)3N4)。
Further optimally, in the second step, the concentration of the graphene oxide in the graphene oxide dispersion liquid is 0.005-0.1 g/mL;
preferably, in the second step, the concentration of carbon nitride in the carbon nitride dispersion liquid in the second step is 8-10 mg/mL;
further optimally, in the second step d, the concentration of the CTAB solution is 0.005-0.01 g/mL;
the application of the catalyst with the adsorption and photocatalysis functions is to treat pollutants hexavalent chromium and methyl blue in sewage by using the catalyst with the adsorption and photocatalysis functions. The specific method comprises the following steps: adjusting the pH value of sewage to be treated containing hexavalent chromium and methyl blue to 2-6, adding a catalyst with double functions of adsorption and photocatalysis into the sewage to be treated according to the proportion that 0.5-1 g of the catalyst with double functions of adsorption and photocatalysis is added into every 1L of the sewage to be treated, irradiating for 2-3 hours in natural light or a xenon lamp light source, and finishing the treatment of the sewage containing hexavalent chromium and methyl blue through the adsorption and photocatalysis effects.
The catalyst with the double functions of adsorption and photocatalysis is g-C uniformly dispersed in graphene oxide with large specific surface area3N4And Co3O4Of a complex of (A) increased g-C3N4And Co3O4The contact area with the target pollutant improves the photocatalytic property, thereby improving the removal efficiency of the target pollutant. The hexavalent chromium treated by the catalyst is reduced into trivalent chromium which can be recycled, the dye is degraded, and the catalyst can be reused for many times. The material of the invention can fully utilize sunlight and can generate substances with oxidation and reduction under visible light, so the photocatalyst with adsorption and catalysis double functions has higher reduction capability on heavy metal chromium and obvious oxidative degradation removal capability on methyl blue, and the Co of the invention3O4-g-C3N4The GO catalyst has the adsorption and catalysis characteristics, and has the adsorption characteristic of 20-30% and the photocatalysis characteristic of 70-80% for heavy metal hexavalent chromium. The dual-function catalyst of the invention also has the advantages of good dispersibility and fast action speed.
The catalyst with the adsorption and photocatalysis functions has the advantages of simple preparation process, low preparation cost and mild preparation conditions.
Can be used in the field of treatment of sewage containing heavy metal chromium and/or dye.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst having both adsorption and photocatalytic functions prepared in example 1;
FIG. 2 is an XRD spectrum of the catalyst with dual functions of adsorption and photocatalysis prepared in example 1;
FIG. 3 is a scanning electron micrograph of the catalyst having both adsorption and photocatalytic functions prepared in example 2;
FIG. 4 is an XRD spectrum of the catalyst with dual functions of adsorption and photocatalysis prepared in example 2;
FIG. 5 is a scanning electron micrograph of the catalyst having both adsorption and photocatalytic functions prepared in example 3;
fig. 6 is an XRD spectrum of the catalyst having both adsorption and photocatalysis functions prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to the examples.
Example 1: the preparation method of the catalyst with the adsorption and photocatalysis functions of the embodiment comprises the following steps:
firstly, preparing Graphene Oxide (GO):
dispersing 1g of graphite worms in 25mL of 98% concentrated sulfuric acid, transferring the graphite worms to an ice-water mixture at a temperature below 10 ℃, adding 0.5g of sodium nitrate, adding 3g of potassium permanganate under the condition of magnetic stirring, and reacting for 3-5 hours; transferring the mixture into a 35 ℃ water bath after the reaction is finished, stirring the mixture for reaction for 30 minutes, adding 45mL of distilled water for dilution, transferring the mixture into an 80 ℃ water bath for reaction for 10 minutes, then adding 60mL of water for dilution, keeping the mixture static for 2 minutes, removing the water bath, cooling the mixture to 25 ℃, adding 10 mass percent of H2O2Until the color becomes golden yellow, then centrifugally separating out a solid phase, washing the solid phase with 5% hydrochloric acid for three times, then washing with ethanol for 2 times, and then freeze-drying for 14 hours at-50 ℃ to obtain graphene oxide;
two, Co3O4-g-C3N4-GO preparation:
a. 0.05g of graphene oxide and 8mg of g-C were weighed3N4Powder, 15mL of N, N-2-methylpyrrolidone, and 2mL of CH3COOH, 0.05g of CTAB, 0.5g of cobalt nitrate and 0.3g of thiourea; wherein the graphene oxide is mixed with g-C3N4The mass ratio of the powder is 1: (0.15 to 0.6);
b. dispersing graphene oxide in 10mL of deionized water to obtain graphene oxide dispersion liquid with the concentration of 0.005 g/mL;
c. dispersing graphite-phase carbon nitride in 10mL of deionized water to obtain carbon nitride dispersion liquid with the concentration of 8 mg/mL;
d. adding CTAB into 10mL of water to prepare a CTAB solution with the concentration of 0.005 g/mL;
e. ultrasonically mixing the graphene oxide dispersion liquid, the carbon nitride dispersion liquid and the N, N-2-methyl pyrrolidone for 2 hours to obtain a brown solution; will CH3Adding COOH into the mixed solution, and stirring for 3 min; adding CTAB solution and magnetically stirring at room temperature for 10 h; finally, adding cobalt nitrate and thiourea, and continuously stirring for 0.5h to obtain a precursor solution;
f. and adding the precursor solution into a reaction kettle, placing the reaction kettle into a forced air drying oven at the temperature of 180 ℃ for 24 hours, cooling to room temperature, separating out solid substances, washing the solid substances for 3 times respectively by using deionized water and ethanol, and freeze-drying to obtain the catalyst with the adsorption and photocatalysis functions.
Wherein g-C as described in step two3N4The powder was prepared by the following method: grinding and mixing 0.5g of thiourea and 2g of melamine, heating to 500 ℃, keeping for 3 hours, and grinding again to obtain CN powder; adding 2g CN powder into 50mL sodium hydroxide aqueous solution with the concentration of 3mol/L, stirring for 1 hour at the temperature of 70 ℃, performing ultrasonic dispersion treatment for 1 hour, repeating stirring and ultrasonic dispersion treatment for 4 times, finally washing with ethanol and deionized water to be neutral, centrifugally separating out solid phase, and drying at 100 ℃ for 6 hours to obtain graphite-phase carbon nitride (g-C)3N4)。
The scanning electron microscope photograph of the catalyst with the adsorption and photocatalytic dual functions prepared in the embodiment is shown in fig. 1, and as can be seen from fig. 1, the dispersibility of cobaltosic oxide particles on the surface of graphene oxide is good, but the particle sizes of the cobaltosic oxide particles are not uniform and regular;
the XRD spectrum of the catalyst with the functions of adsorption and photocatalysis prepared in the embodiment is shown in figure 2, and as can be seen from figure 2, the crystal form of the carbon nitride is not changed after treatment, and the peak of cobaltosic oxide is not sharp.
The method for treating the sewage containing hexavalent chromium and methyl blue by using the catalyst with the adsorption and photocatalysis functions, which is prepared by the embodiment, comprises the following steps: the concentration of hexavalent chromium and the concentration of methyl blue in the sewage to be treated are respectively 20mg/L and 20 mg/L; taking 20mL of sewage to be treated, adjusting the pH value of the sewage to be treated to be 6, adding 10mg of the catalyst with the double functions of adsorption and photocatalysis prepared in the embodiment, standing for 30min under a dark condition, transferring to a xenon lamp with a light source of 100W, continuously irradiating for 150min, respectively measuring 2mL of sewage every 30min during treatment, centrifuging, and then detecting the concentrations of residual hexavalent chromium and methyl blue in the solution by using an ultraviolet spectrophotometer. Calculation shows that after the treatment of placing under dark conditions, the removal rates of hexavalent chromium and methyl blue are respectively 25% and 18%, and after 150min irradiation treatment, the removal rates of hexavalent chromium and methyl blue respectively reach 82% and 79%.
In addition, the treatment test under natural light is carried out in parallel, and the specific method comprises the following steps: the concentration of hexavalent chromium and the concentration of methyl blue in the sewage to be treated are respectively 20mg/L and 20 mg/L; taking 20mL of sewage to be treated, adjusting the pH value of the sewage to be 6, adding 10mg of the catalyst with the double functions of adsorption and photocatalysis prepared in the embodiment, standing for 30min under dark conditions, transferring to natural light, standing for 150min, respectively measuring 2mL of sewage every 30min, centrifuging, and detecting the concentrations of residual hexavalent chromium and methyl blue in the solution by using an ultraviolet spectrophotometer. Calculation shows that after the treatment of placing in the dark and the natural light irradiation treatment for 150min, the removal rates of hexavalent chromium and methyl blue respectively reach 80% and 76%.
Example 2: the preparation method of the catalyst with the adsorption and photocatalysis functions of the embodiment comprises the following steps:
firstly, preparing Graphene Oxide (GO):
dispersing 1.5g of flake graphite in 30mL of concentrated sulfuric acid with the mass percentage concentration of 98%, transferring the flake graphite to an ice water mixture with the temperature of below 10 ℃, adding 0.7g of sodium nitrate, adding 5g of potassium permanganate under the condition of magnetic stirring, and reacting for 4 hours; transferring the mixture into a 35 ℃ water bath after the reaction is finished, stirring the mixture for reaction for 45 minutes, adding 50mL of distilled water for dilution, transferring the mixture into an 80 ℃ water bath for reaction for 20 minutes, then adding 75mL of water for dilution, keeping the mixture static for 4 minutes, removing the water bath, cooling the mixture to 25 ℃, adding 10 mass percent of H2O2Until the color turned to golden yellow, the solid phase was centrifuged, and 5% of the solid phase was usedWashing with hydrochloric acid for 3 times, then washing with ethanol for 2 times, and then freeze-drying for 14 hours at-50 ℃ to obtain graphene oxide;
two, Co3O4-g-C3N4-GO preparation:
a. 0.075g of graphene oxide, 13.5mg of g-C are weighed3N4Powder, 17mL of N, N-2-methylpyrrolidone, and 3mL of CH3COOH, 0.07g CTAB, 0.75g cobalt nitrate and 0.4g thiourea;
b. dispersing graphene oxide in 12mL of deionized water to obtain graphene oxide dispersion liquid with the concentration of 0.005 g/mL;
c. dispersing graphite-phase carbon nitride in 1.5mL of deionized water to obtain 9mg/mL carbon nitride dispersion liquid;
d. adding CTAB into 12mL of water to prepare a CTAB solution with the concentration of 0.005 g/mL;
e. ultrasonically mixing the graphene oxide dispersion liquid, the carbon nitride dispersion liquid and the N, N-2-methyl pyrrolidone for 3 hours to obtain a brown solution; will CH3Adding COOH into the mixed solution, and stirring for 4 min; adding CTAB solution and magnetically stirring at room temperature for 11 h; finally, adding cobalt nitrate and thiourea, and continuously stirring for 45min to obtain a precursor solution;
f. and adding the precursor solution into a reaction kettle, putting the reaction kettle into a furnace with the temperature of 190 ℃ for keeping for 24 hours, cooling to room temperature, separating out solid phase substances, washing the solid phase substances for 3 times respectively by using deionized water and ethanol, and freeze-drying to obtain the catalyst with the adsorption and photocatalysis functions.
Wherein g-C as described in step two3N4The powder was prepared by the following method: grinding and mixing 1.5g of thiourea and 4g of melamine, heating to 550 ℃, keeping for 4 hours, and grinding again to obtain CN powder; adding 3g CN powder into 60mL sodium hydroxide aqueous solution with the concentration of 3mol/L, stirring for 2 hours at the temperature of 80 ℃, performing ultrasonic dispersion treatment for 2 hours, repeating stirring and ultrasonic dispersion treatment for 4 times, finally washing with ethanol and deionized water to be neutral, then centrifugally separating out solid phase, and drying at 105 ℃ for 7 hours to obtain graphite-phase carbon nitride (g-C)3N4)。
The scanning electron microscope photograph of the catalyst with the adsorption and photocatalytic functions prepared in this example is shown in fig. 3, and as can be seen from fig. 3, the distribution of cobaltosic oxide on graphene oxide is relatively uniform, and the particle size is regular as compared with that in example 1;
the XRD spectrum of the catalyst with the functions of adsorption and photocatalysis prepared in the embodiment is shown in figure 4, and as can be seen from figure 4, along with the increase of various raw materials, the crystallinity of cobaltosic oxide tends to be better, and the peak type is sharper than that of the catalyst in the embodiment 1.
The method for treating the sewage containing hexavalent chromium and methyl blue by using the catalyst with the adsorption and photocatalysis functions, which is prepared by the embodiment, comprises the following steps: the concentration of hexavalent chromium and the concentration of methyl blue in the sewage to be treated are respectively 20mg/L and 20 mg/L; taking 20mL of sewage to be treated, adjusting the pH value of the sewage to be treated to be 4, adding 15mg of the catalyst with the double functions of adsorption and photocatalysis prepared in the embodiment, standing for 30min under a dark condition, transferring to a xenon lamp with a light source of 100W, continuously irradiating for 150min, measuring 2mL of sewage every 30min during the period, centrifuging, and detecting the concentrations of residual hexavalent chromium and methyl blue in the solution by using an ultraviolet spectrophotometer. Calculation shows that after the treatment of placing under dark conditions, the removal rates of hexavalent chromium and methyl blue are respectively 28% and 21%, and after the irradiation treatment of 150min, the removal rates of hexavalent chromium and methyl blue are respectively 91% and 86%.
In addition, the treatment test under natural light is carried out in parallel, and the specific method comprises the following steps: the concentration of hexavalent chromium and the concentration of methyl blue in the sewage to be treated are respectively 20mg/L and 20 mg/L; taking 20mL of sewage to be treated, adjusting the pH value of the sewage to be treated to be 4, adding 15mg of the catalyst with the double functions of adsorption and photocatalysis prepared in the embodiment, standing for 30min under dark condition, transferring to natural light, standing for 150min, respectively measuring 2mL of sewage every 30min, centrifuging, and detecting the concentrations of residual hexavalent chromium and methyl blue in the solution by using an ultraviolet spectrophotometer. Calculation shows that after the treatment of placing in the dark and the natural light irradiation treatment for 150min, the removal rates of hexavalent chromium and methyl blue reach 89% and 84% respectively.
Example 3: the preparation method of the catalyst with the adsorption and photocatalysis functions of the embodiment comprises the following steps:
firstly, preparing Graphene Oxide (GO):
dispersing 2g of 200-mesh graphite powder in 50mL of 98% concentrated sulfuric acid, transferring the graphite powder to an ice-water mixture at the temperature of below 10 ℃, adding 1g of sodium nitrate, adding 6g of potassium permanganate under the condition of magnetic stirring, and reacting for 5 hours; transferring the mixture into a 35 ℃ water bath after the reaction is finished, stirring the mixture for reaction for 60 minutes, adding 60mL of distilled water for dilution, transferring the mixture into a 90 ℃ water bath for reaction for 30 minutes, then adding 90mL of water for dilution, keeping the mixture static for 8 minutes, removing the water bath, cooling the mixture to 25 ℃, adding 10 mass percent of H2O2Until the color becomes golden yellow, then centrifugally separating out a solid phase, washing the solid phase with 5% hydrochloric acid for 3 times, then washing with ethanol for 2 times, and then freeze-drying for 14 hours at-50 ℃ to obtain graphene oxide;
two, Co3O4-g-C3N4-GO preparation:
a. weigh 1g of graphene oxide, 20mg of g-C3N4Powder, 20mL of N, N-2-methylpyrrolidone, 4mL of CH3COOH, 0.1g CTAB, 1g cobalt nitrate and 0.6g thiourea;
b. dispersing graphene oxide in 15mL of deionized water to obtain graphene oxide dispersion liquid with the concentration of 0.067 g/mL;
c. dispersing graphite-phase carbon nitride in 2mL of deionized water to obtain carbon nitride dispersion liquid with the concentration of 10 mg/mL;
d. adding CTAB into 15mL of water to prepare a CTAB solution with the concentration of 0.005 g/mL;
e. ultrasonically mixing the graphene oxide dispersion liquid, the carbon nitride dispersion liquid and the N, N-2-methyl pyrrolidone for 4 hours to obtain a brown solution; will CH3Adding COOH into the mixed solution, and stirring for 5 min; adding CTAB solution and magnetically stirring at room temperature for 12 h; finally, adding cobalt nitrate and thiourea, and continuously stirring for 60min to obtain a precursor solution;
f. and adding the precursor solution into a reaction kettle, putting the reaction kettle into a furnace with the temperature of 200 ℃ for 24 hours, cooling to room temperature, separating out solid phase substances, washing the solid phase substances for 3 times respectively by using deionized water and ethanol, and freeze-drying to obtain the catalyst with the adsorption and photocatalysis functions.
Wherein g-C as described in step two3N4The powder was prepared by the following method: grinding and mixing 2g of thiourea and 6g of melamine, heating to 600 ℃, keeping for 6 hours, and grinding again to obtain CN powder; adding 4g CN powder into 80mL sodium hydroxide aqueous solution with the concentration of 3mol/L, stirring for 3 hours at the temperature of 90 ℃, performing ultrasonic dispersion treatment for 2 hours, repeating stirring and ultrasonic dispersion treatment for 4 times, finally washing with ethanol and deionized water to be neutral, then centrifugally separating out solid phase, and drying at 105 ℃ for 7 hours to obtain graphite-phase carbon nitride (g-C)3N4)。
The scanning electron micrograph of the catalyst with the adsorption and photocatalytic functions prepared in this example is shown in fig. 5, and it can be seen from fig. 6 that when the addition amount of graphene oxide is 2 times that of the original graphene oxide, cobaltosic oxide still maintains better dispersibility, and the particles are more uniform and regular.
An XRD (X-ray diffraction) spectrum of the catalyst with the adsorption and photocatalysis functions prepared in the embodiment is shown in figure 6, and as can be seen from figure 6, when the addition amount is changed, the crystal form of the original substance in the material is not changed and only the morphology of particles is changed by combining figure 5.
The method for treating the sewage containing hexavalent chromium and methyl blue by using the catalyst with the adsorption and photocatalysis functions, which is prepared by the embodiment, comprises the following steps: the concentration of hexavalent chromium and the concentration of methyl blue in the sewage to be treated are respectively 20mg/L and 20 mg/L; taking 20mL of sewage to be treated, adjusting the pH value of the sewage to be treated to be 2, adding 20mg of the catalyst with the double functions of adsorption and photocatalysis prepared in the embodiment, standing for 30min under a dark condition, transferring to a xenon lamp with a light source of 100W, continuously irradiating for 150min, measuring 2mL of sewage every 30min during the period, centrifuging, and detecting the concentrations of residual hexavalent chromium and methyl blue in the solution by using an ultraviolet spectrophotometer. Calculation shows that the removal rates of hexavalent chromium and methyl blue are respectively 30% and 24% after the treatment of placing under dark conditions, and the removal rates of hexavalent chromium and methyl blue are respectively 100% and 95% after the irradiation treatment of 150min and 150 min.
In addition, the treatment test under natural light is carried out in parallel, and the specific method comprises the following steps: the concentration of hexavalent chromium and the concentration of methyl blue in the sewage to be treated are respectively 20mg/L and 20 mg/L; taking 20mL of sewage to be treated, adjusting the pH value of the sewage to be treated to be 4, adding 15mg of the catalyst with the double functions of adsorption and photocatalysis prepared in the embodiment, standing for 30min under dark condition, transferring to natural light, standing for 150min, respectively measuring 2mL of sewage every 30min, centrifuging, and detecting the concentrations of residual hexavalent chromium and methyl blue in the solution by using an ultraviolet spectrophotometer. Calculation shows that after the treatment of placing in the dark and the natural light irradiation treatment for 150min, the removal rates of hexavalent chromium and methyl blue reach 96% and 89% respectively.
Claims (9)
1. A preparation method of a catalyst with dual functions of adsorption and photocatalysis is characterized by comprising the following steps:
firstly, preparing graphene oxide:
dispersing graphite materials in concentrated sulfuric acid with the mass percentage concentration of 98%, adding sodium nitrate under the condition of keeping the temperature below 10 ℃, adding potassium permanganate under the condition of magnetic stirring, reacting for 3-5 hours, heating to 30-35 ℃ after the reaction is finished, stirring, reacting for 30-60 minutes, adding distilled water for diluting, heating to 70-90 ℃ for reacting for 10-30 minutes, then adding water for diluting, keeping still for 2-8 minutes, cooling to 20-30 ℃, adding H, reacting for 10-30 minutes, adding water for diluting, and keeping still for 2-8 minutes2O2Until the color becomes golden yellow, centrifugally separating out a solid phase, washing the solid phase with 5% hydrochloric acid, then washing with ethanol, and centrifugally freeze-drying to obtain graphene oxide;
two, Co3O4-g-C3N4-GO preparation:
a. weighing graphene oxide, graphite-phase carbon nitride powder, N-2-methyl pyrrolidone, acetic acid, hexadecyl trimethyl ammonium bromide, cobalt nitrate and thiourea; wherein the graphene oxide is mixed with g-C3N4Of powdersThe mass ratio is 1: (0.15 to 0.6); the ratio of the mass of graphene oxide to the volume of N, N-2-methylpyrrolidone was 1 g: (300-400) mL; mass of graphene oxide and CH3Volume ratio of COOH 1 g: (40-80) mL; the mass ratio of the graphene oxide to CTAB is 1: (1-2); the mass ratio of the graphene oxide to the cobalt nitrate is 1: (10-20); the mass ratio of the graphene oxide to the thiourea is 1: (6-12);
b. dispersing graphene oxide in deionized water to obtain a graphene oxide dispersion liquid;
c. dispersing graphite-phase carbon nitride in deionized water to obtain carbon nitride dispersion liquid;
d. adding cetyl trimethyl ammonium bromide into the ionized water to prepare a CTAB solution;
e. ultrasonically mixing the graphene oxide dispersion liquid, the carbon nitride dispersion liquid and N, N-2-methyl pyrrolidone for 2-4 hours to obtain a mixed liquid; will CH3Adding COOH into the mixed solution and stirring for 3-5 min; adding a CTAB solution and stirring for 10-12 h; finally, adding cobalt nitrate and thiourea, and continuously stirring for 0.5-1 h to obtain a precursor solution;
f. adding the precursor solution into a reaction kettle, placing the reaction kettle into a forced air drying oven at the temperature of 180-200 ℃ for 24-28 h, cooling to room temperature, separating out solid phase substances, washing with deionized water and ethanol, and freeze-drying to obtain a catalyst with adsorption and photocatalysis functions; the catalyst is compounded by cobaltosic oxide, graphite phase carbon nitride and graphene oxide.
2. The method for preparing a catalyst with dual functions of adsorption and photocatalysis according to claim 1, wherein the graphite-like material in the first step is graphite, graphite worms or flake graphite.
3. The method for preparing a catalyst with dual functions of adsorption and photocatalysis according to claim 1 or 2, characterized in that the ratio of the mass of the graphite-like material to the volume of concentrated sulfuric acid with a mass percent concentration of 98% in the first step is 1 g: (20-50) mL.
4. The method for preparing a catalyst with dual functions of adsorption and photocatalysis according to claim 1 or 2, characterized in that the mass ratio of the graphite material to the sodium nitrate in the first step is 1: (0.4 to 1).
5. The preparation method of the catalyst with the dual functions of adsorption and photocatalysis according to claim 1 or 2, characterized in that the mass ratio of the graphite material to the potassium permanganate in the step one is 1: (3-6).
6. The method for preparing a catalyst having both functions of adsorption and photocatalysis according to claim 1 or 2, wherein the method for preparing graphite phase carbon nitride in step two a is as follows: thiourea and melamine are mixed according to the mass ratio of 1: (1-12) grinding and mixing, heating to 500-600 ℃, keeping for 3-6 hours, and grinding again to obtain CN powder; according to the proportion of the mass of CN powder to the volume of 3mol/L sodium hydroxide aqueous solution of 1 g: (12-40) mL, adding CN powder into a sodium hydroxide aqueous solution, stirring for 1-4 hours at the temperature of 70-90 ℃, performing ultrasonic dispersion treatment for 1-3 hours, repeating stirring and ultrasonic dispersion treatment for 4-5 times, washing with ethanol and deionized water to be neutral, centrifuging to separate out a solid phase, and drying at the temperature of 100-110 ℃ for 6-8 hours to obtain graphite-phase carbon nitride (g-C)3N4）。
7. The preparation method of the catalyst with the dual functions of adsorption and photocatalysis according to claim 1 or 2, characterized in that the graphene oxide concentration in the graphene oxide dispersion liquid in the step two is 0.005-0.1 g/mL.
8. The preparation method of the catalyst with the functions of both adsorption and photocatalysis according to claim 1 or 2, characterized in that the carbon nitride concentration in the carbon nitride dispersion liquid in the second step c is 8-10 mg/mL.
9. The use of the catalyst having both adsorption and photocatalysis functions prepared by the method of claim 1, characterized in that the use is to treat pollutants hexavalent chromium and methyl blue in sewage by using the catalyst having both adsorption and photocatalysis functions; the specific method comprises the following steps: adjusting the pH value of sewage to be treated containing hexavalent chromium and methyl blue to 2-6, adding a catalyst with double functions of adsorption and photocatalysis into the sewage to be treated according to the proportion that 0.5-1 g of the catalyst with double functions of adsorption and photocatalysis is added into every 1L of the sewage to be treated, irradiating for 2-3 hours in natural light or a xenon lamp light source, and finishing the treatment of the sewage containing hexavalent chromium and methyl blue through the adsorption and photocatalysis effects.
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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 |
| CN110302767A (en) * | 2019-07-03 | 2019-10-08 | 瑞德纳米科技（广州）有限公司 | It is a kind of for removing the composite material of heavy metal ion in water |
| CN111617763B (en) * | 2020-05-12 | 2022-08-16 | 大连理工大学 | Method for preparing catalyst by anchoring cobaltosic oxide through graphene oxide epoxy group |
| CN111760555B (en) * | 2020-06-08 | 2023-03-14 | 天津科技大学 | Preparation method and application of ZIF-based low-temperature adsorption material |
| 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 |
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