CN108246334B - Functionalized ternary composite photocatalytic material and preparation method and application thereof - Google Patents
Functionalized ternary composite photocatalytic material and preparation method and application thereof Download PDFInfo
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 22
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/10—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention relates to a functionalized ternary composite photocatalytic material and a preparation method and application thereof. The functionalized ternary composite photocatalytic material prepared by the invention can effectively remove hexavalent chromium ions in water, and the pH value of the solution and the background electrolyte can influence the removal performance of the functionalized ternary composite photocatalytic material. The method can be used for treating the chromium-containing wastewater discharged by electroplating plants, smelting plants, electronic plants and the like.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials and water treatment, and particularly relates to a functionalized ternary composite photocatalytic material and a preparation method and application thereof.
Background
At present, the heavy metal pollution problem in China is prominent. With the rapid development of industry, a large amount of heavy metal pollutants are discharged into water bodies in various ways, the heavy metal pollution of the water bodies is difficult to control, and the safety of agricultural and sideline products is affected even in places with serious pollution. Therefore, an efficient and economical technology for treating wastewater discharged by enterprises is urgently needed to be found. We generally use ion exchange, adsorption, redox, electrodeposition, filtration, chemical precipitation, osmosis, etc. methods for wastewater treatment. In recent years, the photocatalysis method for treating heavy metal wastewater enters the sight of people. The photocatalysis method has the advantages of normal temperature and pressure, no toxicity, high speed, high efficiency, good selectivity, low energy consumption and the like, and the attention is increasingly paid. Although most photocatalytic reductive degradation of heavy metal ions in wastewater is still in the laboratory research stage, more and more research is being conducted on the aspect. The types and catalytic efficiency of the currently used photocatalysts are limited. Therefore, research and development of novel photocatalysts with high catalytic amount, high efficiency and low cost and practicability become a key scientific and technical problem for further development and application of the photocatalytic method.
Graphite phase carbon nitride (g-C)3N4) The polymer semiconductor has a unique electronic band structure and excellent chemical stability, can be used as a visible light photocatalyst, is widely applied to the photocatalytic conversion of solar energy due to the characteristics of low price, stability, no metal component and the like, and attracts people's extensive attention such as degradation of organic pollutants, selective photosynthesis, photolysis of water to generate hydrogen and the like. g-C3N4The photocatalyst is cheap and stable, meets the basic requirements of the photocatalyst, has the characteristics of easily regulated energy band structure, chemical composition of polymer semiconductors and the like, and is a research direction worthy of being deeply explored. g-C3N4Also has the characteristics of strong reduction capability of conduction band electrons and weak oxidation capability of valence band holes, g-C3N4Can also be usedTo activate molecular oxygen to generate superoxide radical (O)2-). Due to g-C3N4The catalyst has the advantages of high exciton binding energy of a photon-generated carrier, serious recombination of photon-generated electron holes, low quantum efficiency, small specific surface area, large forbidden band width, unfavorable solid-liquid separation after the catalysis is finished, unfavorable recovery of the catalyst and the like, limits the application of the catalyst in the field of photocatalysis, and cannot be popularized and applied in large scale in practical engineering due to recombination. Magnetic bismuth ferrite, graphene oxide with strong electric conductivity and g-C3N4The composite material can improve the separating capacity and the photocatalysis capacity. The composite pollutant is used for removing hexavalent chromium in water through photocatalytic reduction, and an effective technical reference can be provided for the treatment of heavy metal wastewater.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the technical problems in the prior art, a functionalized ternary composite photocatalytic material which has strong catalytic performance and high efficiency and can be used for photocatalytic treatment of heavy metal ions is developed.
The invention provides a preparation method of a functionalized ternary composite photocatalytic material, which is characterized in that bismuth ferrite and carbon nitride are loaded on graphene oxide, and the prepared functionalized ternary composite photocatalytic material can realize rapid separation and increase the oxidation reduction capability through an external magnetic field, and comprises the following specific steps:
(1) weighing 20-80 g of melamine in a crucible, adding distilled water to enable the melamine to be submerged in a medicine, standing for layering, pouring out a supernatant, adding absolute ethyl alcohol to enable the melamine to be submerged in the medicine, standing, pouring out the supernatant after layering, putting the crucible into a muffle furnace, heating for 10-60 min at 40-100 ℃ without covering a cover, covering the crucible with the cover, heating for 2-6 hours at 400-800 ℃, cooling to room temperature, grinding and screening to obtain carbon nitride;
(2) mixing graphite powder and K2S2O4And P2O5Adding the graphite powder and K into 10-50 mL of concentrated sulfuric acid to react for 2-8 hours at 50-100 DEG C2S2O4And P2O5The mass ratio of (1): (0.5-2): (0.5-2), wherein the concentration of the concentrated sulfuric acid is 9098 percent, cooling to 20-40 ℃, adding 800-1200 mL of ultrapure water, standing for 8-12 hours, washing the product to be neutral, and drying at 40-80 ℃ to obtain pre-oxidized graphite;
(3) adding the pre-oxidized graphite obtained in the step (2) into 200-300 mL of concentrated sulfuric acid, and then adding NaNO3And KMnO4The concentration of the concentrated sulfuric acid is 90-98%, and the pre-oxidized graphite and NaNO are3And KMnO4The mass ratio of (1): (0.5-2): (10-50), reacting for 2-6 hours at 0-5 ℃, heating to 30-40 ℃, reacting for 1-4 hours, adding 200-800 mL of ultrapure water, reacting for 1-6 hours at 80-100 ℃, then adding 800-1200 mL of ultrapure water and 20-60 mLH2O2Said H is2O2The concentration is 20-30%, the reaction is continued for 1-6 hours, the obtained product is washed by an HCl solution with the concentration of 5-15%, then a large amount of water is used for washing to be neutral, and the graphene oxide aqueous suspension is obtained through ultrasonic dispersion for 1-4 hours at the temperature of 30-60 ℃;
(4) dissolving ferric nitrate and bismuth nitrate into 100-300 mL of ethylene glycol monomethyl ether, adding 0.1-0.5 mL of nitric acid, and dissolving citric acid into 50-200 mL of ethylene glycol, wherein the mass ratio of the ferric nitrate to the bismuth nitrate to the citric acid is 1: (0.5-2): (0.1-2), mixing the two solutions, heating and stirring the two solutions at the temperature of 40-80 ℃ for 1-4 hours, heating the heated and stirred solution at the temperature of 50-150 ℃ for 6-13 hours to obtain light brown gel, pouring the obtained gel into a crucible, heating the gel at the temperature of 100-320 ℃ for 10-40 min, calcining the gel at the temperature of 300-800 ℃ for 1-5 hours, cooling and grinding to obtain bismuth ferrite;
(5) dissolving the carbon nitride obtained in the step (1), the graphene oxide obtained in the step (3) and the bismuth ferrite obtained in the step (4) in 100-400 mL of methanol, wherein the mass ratio of the carbon nitride to the graphene oxide aqueous solution to the bismuth ferrite is 1: (20-50): (0.5-2), ultrasonically dispersing for 1-6 hours at the temperature of 30-80 ℃, and drying for 3-8 hours in an oven at the temperature of 50-100 ℃ to obtain the functionalized ternary composite photocatalytic material.
The invention also provides a method for applying the functionalized ternary composite photocatalytic material to removing heavy metal ions in water, which comprises the following steps: taking a certain amount of hexavalent chromium wastewater, wherein the concentration of hexavalent chromium in the wastewater is 0.001-0.1 g/L, adjusting the pH value to 1-12, adding a certain amount of functionalized ternary composite photocatalytic material into the wastewater, wherein the addition amount of each liter of wastewater is 0.05-3 g by weight of the functionalized ternary composite photocatalytic material, reacting for 0-8 hours on a magnetic stirrer with the rotating speed of 500-2000 rpm, adding light for reaction after a certain time, sampling once every other time, wherein the time intervals of every two samples are the same, and separating the functionalized ternary composite photocatalytic material from the solution by using a magnet after the reaction is finished, so as to finish the removal of hexavalent chromium in the wastewater.
Compared with the prior art, the invention has the advantages that:
1. the raw materials used in the preparation process of the functionalized ternary composite photocatalytic material are wide in source and low in price, and the main raw materials are common chemical products.
2. The product prepared by the method is non-toxic and environment-friendly.
3. The functionalized ternary composite photocatalytic material has the advantages of simple preparation process, convenient operation and easy realization of industrial production.
4. The functionalized ternary composite photocatalytic material has high photocatalytic efficiency on heavy metal ions in water, and can be easily separated from the treated solution and reused. Provides a new way for the treatment of heavy metal pollution in the wastewater and the resource utilization of heavy metal.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a functionalized three-way composite photocatalytic material of example 1 of the present invention.
Detailed Description
The invention will be described in further detail below with reference to the drawings and specific examples.
Example 1:
the invention relates to a preparation method of a functionalized ternary composite photocatalytic material, which comprises the following steps:
weighing 30g of melamine in a crucible, adding distilled water to enable the melamine to be submerged in a medicine, standing for layering, pouring out a supernatant, adding absolute ethyl alcohol to enable the melamine to be submerged in the medicine, standing, pouring out the supernatant after layering, putting the crucible into a muffle furnace, heating for 40min at 70 ℃ without covering a cover, covering the crucible with the cover, heating for 3 hours at 600 ℃, cooling to room temperature, grinding and screening to obtain the carbon nitride.
Mixing 6g of graphite powder and 5g K2S2O8And 5g P2O5Adding the solution into 24mL of concentrated sulfuric acid with the mass concentration of 98%, reacting at 80 ℃ for 4.5 hours, cooling to room temperature, adding 1000mL of ultrapure water, standing for 12 hours, washing the product to be neutral, and drying at 60 ℃ to obtain pre-oxidized graphene; adding the obtained pre-oxidized graphite into 240mL of concentrated sulfuric acid with the mass concentration of 98%, and then adding 5g of NaNO3And 30g KMnO4Reacting at 0 deg.C for 4 hr, heating to 35 deg.C for 2 hr, adding 500mL of ultrapure water, reacting at 98 deg.C for 1 hr, adding 1000mL of ultrapure water and 40mLH2O2And continuing to react for 2 hours, washing the obtained product with a 10% HCl solution, washing the product with a large amount of water to be neutral, and performing ultrasonic dispersion at 50 ℃ for 2 hours to obtain a graphene oxide aqueous suspension with the mass concentration of 5 mg/mL.
32.3192g of ferric nitrate and 38.8064g of bismuth nitrate are dissolved in 200mL of ethylene glycol monomethyl ether, 0.2mL of 0.1mol/L nitric acid is added, citric acid is dissolved in 100mL of ethylene glycol, the two solutions are mixed and heated and stirred at 60 ℃ for 1 hour, the heated and stirred solution is heated at 100 ℃ for 10 hours to obtain light brown gel, the obtained gel is poured into a crucible, heated at 200 ℃ for 30min and then calcined at 500 ℃ for 2 hours, and the mixture is cooled and ground to obtain the bismuth ferrite.
And dissolving 3g of the obtained carbon nitride, 29mL of graphene oxide aqueous solution and 3g of bismuth ferrite in 100mL of methanol, performing ultrasonic dispersion for 3 hours at 50 ℃, and drying for 6 hours at 80 ℃ in an oven to obtain the functionalized ternary composite photocatalytic material.
The prepared functionalized ternary composite photocatalytic material is brown in appearance, and the structure of the material is shown in figure 1 when the material is placed under a scanning electron microscope, so that the three materials can be well compounded.
Example 2:
the functionalized ternary composite photocatalytic material is used for removing heavy metal ions in water, and comprises the following steps:
taking 200mL of hexavalent chromium wastewater with the concentration of 5mg/L, adjusting the pH value of the hexavalent chromium wastewater with hydrochloric acid or sodium hydroxide within the range of 2-8, adding the functionalized ternary composite photocatalytic material prepared in the embodiment 1 into a wastewater sample, wherein the addition amount of each liter of wastewater is 2.5g based on the weight of the functionalized ternary composite photocatalytic material, placing a reactor on a magnetic stirrer with the rotating speed of 1000rpm for reaction, sampling once every 20min, adding light after 1 hour for reaction, and keeping the reaction for 3 hours. The concentration of hexavalent chromium ions in the sample was measured using ultraviolet spectrophotometry, and the calculated removal rate results are shown in table 1.
Table 1: influence of pH value on removal of hexavalent chromium ions in water by functionalized ternary composite material
| pH value | 2 | 4 | 6 | 8 |
| Hexavalent chromium removal (%) | 100％ | 72.8％ | 39.55％ | 35.2％ |
As can be seen from Table 1, the removal amount of hexavalent chromium ions by the functionalized ternary composite material decreases with increasing pH, and reaches a balance when the pH is less than or equal to 2.
Example 3:
the functionalized ternary composite photocatalytic material is used for removing heavy metal ions in water, and comprises the following steps:
the functionalized ternary composite photocatalytic material prepared in example 1 is respectively added into a volume of 200mL, the initial pH is 2, the background electrolyte with the molar concentration of 0.005mol/L is Na2SO4、CaCl2And NaNO3The initial concentration of hexavalent chromium ions in the hexavalent chromium wastewater is 5mg/L, the addition amount of each liter of wastewater is 2.5g based on the weight of the functionalized ternary composite photocatalytic material, the reactor is placed on a magnetic stirrer with the rotating speed of 1000rpm for reaction, a sample is taken once every 20min (about 5mL), and after 1 hour, illumination is added for reaction, and the reaction lasts for 3 hours. The concentration of hexavalent chromium ions in the sample was measured using ultraviolet spectrophotometry, and the calculated removal rate results are shown in table 2.
Table 2: influence of background electrolyte on removal of hexavalent chromium ions in water by functionalized ternary composite material
| Background electrolyte | Is free of | Na2SO4 | CaCl2 | NaNO3 |
| Hexavalent chromium removal (%) | 92.35％ | 79.3％ | 95.25％ | 84.35％ |
As can be seen from Table 2, three kinds of background electrolytes have an effect on the removal of hexavalent chromium ions from the functionalized ternary composite material, wherein Na has an effect2SO4And NaNO3Will inhibit the removal of hexavalent chromium, and CaCl2The removal of hexavalent chromium is promoted.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and various process schemes having no substantial difference from the concept of the present invention are within the protection scope of the present invention.
Claims (1)
1. A method for applying a functionalized ternary composite photocatalytic material to removal of heavy metal ions in water comprises the following steps: adding the functionalized ternary composite photocatalytic material into 200mL of CaCl serving as a background electrolyte with initial pH of 2 and molar concentration of 0.005mol/L2In the hexavalent chromium wastewater, the initial concentration of hexavalent chromium ions is 5mg/L, the addition amount of each liter of wastewater is 2.5g based on the weight of the functionalized ternary composite photocatalytic material, the reactor is placed on a magnetic stirrer with the rotating speed of 1000rpm for reaction, a sample is taken once every 20min, 5mL of the sample is taken once, after 1 hour, illumination is added for reaction, and the reaction lasts for 3 hours; after the reaction is finished, separating the functionalized ternary composite photocatalytic material from the solution by using a magnet to finish the removal of hexavalent chromium in the wastewater;
the functionalized ternary composite photocatalytic material takes graphene oxide as a matrix, and carbon nitride and bismuth ferrite particles are loaded on the matrix;
the preparation method of the functionalized ternary composite photocatalytic material comprises the following steps:
(1) weighing 20-80 g of melamine in a crucible, adding distilled water to enable the melamine to be submerged in a medicine, standing for layering, pouring out a supernatant, adding absolute ethyl alcohol to enable the melamine to be submerged in the medicine, standing, pouring out the supernatant after layering, putting the crucible into a muffle furnace, heating for 10-60 min at 40-100 ℃ without covering a cover, covering the crucible with the cover, heating for 2-6 hours at 400-800 ℃, cooling to room temperature, grinding and screening to obtain carbon nitride;
(2) mixing graphite powder and K2S2O4And P2O5Adding the graphite powder and K into 10-50 mL of concentrated sulfuric acid to react for 2-8 hours at 50-100 DEG C2S2O4And P2O5The mass ratio of (1): (0.5-2): (0.5-2), cooling the concentrated sulfuric acid to 20-40 ℃, adding 800-1200 mL of ultrapure water, standing for 8-12 hours, washing the product to be neutral, and drying at 40-80 ℃ to obtain pre-oxidized graphite;
(3) adding the pre-oxidized graphite obtained in the step (2) into 200-300 mL of concentrated sulfuric acid, and then adding NaNO3And KMnO4The concentration of the concentrated sulfuric acid is 90-98%, and the pre-oxidized graphite and NaNO are3And KMnO4The mass ratio of (1): (0.5-2): (10-50), reacting for 2-6 hours at 0-5 ℃, heating to 30-40 ℃, reacting for 1-4 hours, adding 200-800 mL of ultrapure water, reacting for 1-6 hours at 80-100 ℃, then adding 800-1200 mL of ultrapure water and 20-60 mLH2O2Said H is2O2The concentration is 20-30%, the reaction is continued for 1-6 hours, the obtained product is washed by an HCl solution with the concentration of 5-15%, then a large amount of water is used for washing to be neutral, and the graphene oxide aqueous suspension is obtained through ultrasonic dispersion for 1-4 hours at the temperature of 30-60 ℃;
(4) dissolving ferric nitrate and bismuth nitrate into 100-300 mL of ethylene glycol monomethyl ether, adding 0.1-0.5 mL of nitric acid, and dissolving citric acid into 50-200 mL of ethylene glycol, wherein the mass ratio of the ferric nitrate to the bismuth nitrate to the citric acid is 1: (0.5-2): (0.1-2), mixing the two solutions, heating and stirring the two solutions at the temperature of 40-80 ℃ for 1-4 hours, heating the heated and stirred solution at the temperature of 50-150 ℃ for 6-13 hours to obtain light brown gel, pouring the obtained gel into a crucible, heating the gel at the temperature of 100-320 ℃ for 10-40 min, calcining the gel at the temperature of 300-800 ℃ for 1-5 hours, cooling and grinding to obtain bismuth ferrite;
(5) dissolving the carbon nitride obtained in the step (1), the graphene oxide obtained in the step (3) and the bismuth ferrite obtained in the step (4) in 100-400 mL of methanol, wherein the mass ratio of the carbon nitride to the graphene oxide aqueous solution to the bismuth ferrite is 1: (20-50): (0.5-2), ultrasonically dispersing for 1-6 hours at the temperature of 30-80 ℃, and drying for 3-8 hours in an oven at the temperature of 50-100 ℃ to obtain the functionalized ternary composite photocatalytic material.
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| CN109174154B (en) * | 2018-09-13 | 2020-08-11 | 浙江大学 | Nitrogen carbide doping modification method and application of nitrogen carbide doping modification method in degradation of antibiotics in wastewater |
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| CN110813354A (en) * | 2019-11-11 | 2020-02-21 | 西安石油大学 | g-C3N4Preparation method of/ZnO/GO ternary composite material and method for degrading methyl orange |
| CN114308097A (en) * | 2021-12-06 | 2022-04-12 | 哈尔滨学院 | Preparation method of nitrogen/bismuth ferrite-graphene composite material |
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