CN111229268B - Full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for well drilling waste liquid treatment, and preparation method and application thereof - Google Patents
Full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for well drilling waste liquid treatment, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 114
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 114
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 89
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 86
- 229940019931 silver phosphate Drugs 0.000 title claims abstract description 86
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- 239000002245 particle Substances 0.000 claims description 13
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- 239000002135 nanosheet Substances 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
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- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 5
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- 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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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for well drilling waste liquid treatment, and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding carbon nanotube sponge into silver nitrate organic alcohol aqueous solution, adding disodium hydrogen phosphate solution, and carrying out hydrothermal reaction on the obtained mixed solution; filtering, washing and drying to obtain the silver phosphate/carbon nano tube sponge composite material; adding sodium bismuthate into a sodium hydroxide solution, then adding a silver phosphate/carbon nano tube sponge composite material, and carrying out hydrothermal reaction; filtering, washing, and freeze drying. The bismuth oxide/silver phosphate/carbon nanotube sponge three-dimensional composite photocatalyst prepared by the invention has the advantages of full spectral response, high photocatalytic activity, low photo-generated electron-hole recombination rate and strong adsorption and degradation capability on nonpolar substances, and is used for in-situ treatment of organic pollution such as polycyclic aromatic hydrocarbon in drilling waste liquid under irradiation of visible light and near infrared light.
Description
Technical Field
The invention relates to a full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for well drilling waste liquid treatment, a preparation method and application thereof, and belongs to the field of well drilling waste liquid treatment.
Background
With the increasing rise of the drilling depth and difficulty, the types and the dosage of chemical additives in the drilling fluid are more and more, so that the treatment difficulty of the waste drilling fluid is increased sharply. In 2019, the drilling operation amount of China can reach 1.95 ten thousand ports, and at least 500 ten thousand tons of waste drilling fluid are generated every year. During the drilling process, a large amount of oil-based lubricant which is commonly added for improving the performance of the drilling fluid, or crude oil mixed into the drilling fluid during drilling into an oil layer and the like can cause the content of polycyclic aromatic hydrocarbon in the waste drilling fluid to be higher. At present, solid-liquid separation, gel breaking flocculation, fine filtration and other pretreatment are commonly adopted, and then degradation is carried out through catalytic oxidation, but the method has the defects of low polycyclic aromatic hydrocarbon removal rate, huge energy consumption, secondary pollution and the like.
The photocatalytic technology for degrading organic pollutants in water is a novel green and efficient water treatment method, becomes a research hotspot due to the extremely high catalytic activity of the organic pollutants, and is a high-efficiency photocatalyst. For example: the quantum efficiency of the silver-based catalyst represented by silver phosphate is as high as 92% under visible light with the wavelength of 420nm, however, the silver phosphate is easily reduced by photo-generated electrons to generate a photo-corrosion phenomenon, and the stability and the photocatalytic activity of the silver-based catalyst are seriously reduced. In recent years, bismuth-based photocatalytic materials have been widely used in the field of photocatalysts because of their low cost and good near-infrared response. Wherein, the bismuth oxide is a novel bismuth-based photocatalyst and has good near infrared light response performance. However, the application of bismuth oxide is greatly limited by the problems of small specific surface area, easy recombination of photoproduction electrons and holes, weak performance of a photocatalyst and the like, and bismuth oxide and a silver-based catalyst can form a heterostructure to remarkably enlarge the absorption range of a system to a spectrum and improve the catalytic activity of the system. However, the conventional heterostructure has the defects of low photoproduction electron-hole separation rate, poor adsorption performance of organic matters and the like, and the catalytic activity of the heterostructure is seriously limited. The carbon nanotube sponge is a porous material with a three-dimensional space network structure formed by self-assembly of carbon nanotubes, and has the characteristics of strong lipophilicity, light weight, high porosity, high specific surface area and the like.
However, there are many patent documents on bismuth-based photocatalysts, such as: chinese patent document CN109482210A provides a silver phosphate/bismuth sulfide/bismuth oxide double Z-type photocatalyst and a preparation method thereof, the photocatalyst takes bismuth oxide as a carrier, the surface of the bismuth oxide is modified with bismuth sulfide and silver phosphate, and the preparation method comprises the following steps: (1) preparing a mixed aqueous solution of bismuth oxide and thiourea for hydrothermal reaction to prepare a bismuth sulfide/bismuth oxide compound; (2) and mixing the bismuth sulfide/bismuth oxide compound with a silver nitrate solution, and adding a disodium hydrogen phosphate solution to perform secondary reaction to obtain the silver phosphate/bismuth sulfide/bismuth oxide composite photocatalyst. However, in the invention, the synthesis temperature of bismuth oxide is too high and is a micron-sized smooth block, so that the specific surface area of bismuth oxide is extremely small, and the adsorption performance of bismuth oxide on nonpolar organic molecules is weak, which is not beneficial to improving the photocatalytic activity. Chinese patent document CN109621994A provides a silver phosphate/multiwalled carbon nanotube/bismuth tungstate composite photocatalytic material and a preparation method thereof, wherein the composite photocatalytic material comprises a multiwalled carbon nanotube/bismuth tungstate composite material formed by compounding a carbon nanotube and bismuth tungstate, and silver phosphate is loaded on the composite material. However, the carrier of the catalyst is only based on one-dimensional carbon nanotubes, so that the problems of low specific surface area, weak adsorption capacity to non-polar organic matters and the like exist, and the photocatalytic efficiency is greatly restricted. Meanwhile, the catalyst obtained by the method cannot effectively absorb photons in a full spectrum range, has low photocatalytic activity and does not have good dual effects of adsorption and degradation.
Therefore, the three-dimensional structure photocatalyst with full spectral response, high photocatalytic activity, low photoproduction electron-hole recombination rate and strong adsorption and degradation capability on nonpolar substances is prepared, and has important significance for realizing high-efficiency adsorption and photodegradation treatment of waste drilling fluid and further expanding the application of the photocatalytic technology in drilling fluid treatment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for well drilling waste liquid treatment, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for well drilling waste liquid treatment is formed by self-assembling silver phosphate, bismuth oxide and carbon nanotube sponge, wherein the silver phosphate and the bismuth oxide are loaded on the carbon nanotube sponge.
According to the invention, the particle size of the silver phosphate is preferably 200-500nm, and more preferably 300-400 nm; the bismuth oxide is micron particles composed of nanosheets with the thickness of 10-20 nm, the particle size of the particles is 2-6 microns, and preferably the particle size of the bismuth oxide particles is 3-4 microns; the pore diameter of the carbon nanotube sponge is 0.5-2.0 mu m, the inner diameter of the carbon nanotube in the carbon nanotube sponge is 20-40nm, the further optimization is 20-30 nm, and the thickness of the tube wall is 5-20 nm.
According to the invention, the preparation method of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst comprises the following steps:
(1) adding carbon nanotube sponge into silver nitrate organic alcohol aqueous solution, stirring, then adding disodium hydrogen phosphate solution, and carrying out hydrothermal reaction on the obtained mixed solution; filtering, washing and drying to obtain the silver phosphate/carbon nano tube sponge composite material;
(2) adding sodium bismuthate into a sodium hydroxide solution, stirring, adding the silver phosphate/carbon nano tube sponge composite material obtained in the step (1), and carrying out hydrothermal reaction on the obtained mixed solution; and filtering, washing, freezing and drying to obtain the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst.
According to the present invention, preferably, the carbon nanotube sponge described in step (1) is a sponge body formed by self-assembly of carbon nanotubes and having a three-dimensional network structure, and can be prepared according to the method described in the literature (Gui, x.c., Wei, j.q., Wang, k.l., Cao, a.y., Zhu, h.w., Jia, y., Shu, q.k., Wu, d.h.carbon nanotubes sponges.advanced materials,2010,22(5): one 621.). The obtained carbon nanotube sponge is formed by random self-assembly of carbon nanotubes formed by high-temperature pyrolysis of a carbon source, and the formed carbon nanotubes have super-strong hydrophobicity and strong lipophilicity and show strong adsorbability on nonpolar molecules. Meanwhile, the carbon nano tube has rich active groups such as hydroxyl, carboxyl and the like on the surface, and the three-dimensional space network structure of the carbon nano tube is beneficial to the photocatalyst with different sizes to load on the surface of the photocatalyst to form a composite photocatalyst system with a three-dimensional space network structure.
According to the present invention, preferably, the mass ratio of the carbon nanotube sponge to the silver nitrate in the step (1) is 1:5 to 15.
According to the invention, the mass concentration of the silver nitrate in the silver nitrate organic alcohol aqueous solution in the step (1) is preferably 0.01-0.015 g/mL.
According to the present invention, preferably, the preparation method of the silver nitrate aqueous organic alcohol solution in the step (1) comprises: ultrasonically dispersing silver nitrate into a mixed solvent of organic alcohol and water; the organic alcohol is one or the combination of two of methanol, ethanol, glycol, propanol and n-butanol; the volume ratio of the organic alcohol to the water is 1: 4-10;
further preferably, the organic alcohol is one or a combination of two of methanol, ethanol and ethylene glycol; more preferably one or a combination of two of ethanol and ethylene glycol; most preferred is a combination of ethanol and ethylene glycol, wherein the volume ratio of ethanol to ethylene glycol is 1: 1.
According to the invention, the mass concentration of the disodium hydrogen phosphate solution in the step (1) is preferably 0.005-0.01 g/mL; the mass ratio of the disodium hydrogen phosphate to the silver nitrate is 1: 1-10, more preferably 1: 1-7, even more preferably 1: 2-5, and most preferably 1: 2-3.
According to the present invention, it is preferable that the stirring conditions in the step (1) are: the stirring temperature is 20-25 ℃, the stirring speed is 200-500 r/min, and the stirring time is 0.5-2 h.
According to the invention, the temperature of the hydrothermal reaction in the step (1) is preferably 50-70 ℃, and the hydrothermal reaction time is preferably 2-4 h.
According to the invention, preferably, the filtering, washing and drying in the step (1) are all carried out under a shading condition, the washing is carried out for 3 times by using absolute ethyl alcohol, and the drying is carried out for 3-5 h under vacuum at 70-90 ℃.
According to the invention, preferably, the concentration of the sodium hydroxide solution in the step (2) is 0.3-0.7 mol/L, and the mass ratio of the sodium hydroxide to the sodium bismuthate is 1: 1-5, and more preferably 1: 2-4; the stirring is carried out under the shading condition.
According to the invention, preferably, the mass ratio of the silver phosphate/carbon nanotube sponge composite material to the sodium bismuthate in the step (2) is 1:1 to 5.
According to the present invention, it is preferable that the hydrothermal reaction in step (2) is performed under the following conditions: the temperature is 150-250 ℃, and the reaction time is 5-8 hours.
According to the present invention, preferably, the filtration, washing and freeze-drying in step (2) are all performed under a shading condition; the washing is carried out for three times by using deionized water, and the freeze drying is carried out for 12-24 hours at the temperature of-50 to-60 ℃.
According to the invention, the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst is applied to degrading polycyclic aromatic hydrocarbons in drilling waste liquid under the irradiation conditions of visible light and near infrared light.
According to the application of the invention, preferably, the polycyclic aromatic hydrocarbon is one or the combination of at least two of naphthalene, phenanthrene and pyrene.
The invention has the following technical characteristics and beneficial effects:
1. the invention provides a full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for well drilling waste liquid treatment, which has the characteristics of full-spectrum response and high-efficiency adsorption and photodegradation performances. In the composite photocatalyst, silver phosphate is a visible light response catalyst, and has good absorption performance on visible light with the wavelength of more than 420 nm; the bismuth oxide can absorb near infrared light with the wavelength of more than 780 nm; the carbon nanotube sponge is an excellent semiconductor, can remarkably improve the separation rate of photo-generated electrons and holes, and has good adsorption performance on nonpolar organic molecules. Because the forbidden band width of the silver phosphate is larger than that of the bismuth oxide, when the two catalysts are loaded on the surface of the carbon nano tube, an internal electric field can be formed to improve the separation rate of photo-generated electrons and holes, and further the catalytic activity of the catalysts is improved.
2. The composite photocatalyst provided by the invention uses carbon nanotube sponge with a three-dimensional space network structure as a carrier, and the obtained photocatalyst has a three-dimensional space structure and a higher specific surface area, and improves the adsorption performance on organic matters, so that the adsorption and photodegradation performance of the catalyst is improved.
3. The bismuth oxide/silver phosphate/carbon nanotube sponge three-dimensional composite photocatalyst prepared by the invention has strong adsorbability on nonpolar macromolecules, can efficiently degrade polycyclic aromatic hydrocarbon under the irradiation of visible light and near infrared light, and can be used for in-situ treatment of organic pollution such as polycyclic aromatic hydrocarbon in drilling waste liquid. Experiments prove that under the irradiation of visible light and near infrared light with the wavelength of more than 420nm, the catalyst can degrade more than 90 percent of polycyclic aromatic hydrocarbon within 15min, and has higher degradation performance.
4. The preparation method of the full-spectrum response composite photocatalyst has the advantages of mild reaction conditions, simple process flow, environmental protection, low energy consumption and the like, and is suitable for industrial production.
Drawings
Fig. 1 is an X-ray diffraction pattern of the carbon nanotube sponge used in the examples, the silver phosphate photocatalyst prepared in comparative example 1, the bismuth oxide photocatalyst prepared in comparative example 2, and the full spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in examples 1 to 3, in which CNT is a carbon nanotube sponge.
Fig. 2 is an infrared spectrum of the carbon nanotube sponge used in the examples, the silver phosphate photocatalyst prepared in comparative example 1, the bismuth oxide photocatalyst prepared in comparative example 2, and the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in example 1, in which CNT is a carbon nanotube sponge.
FIG. 3 is a scanning electron micrograph of the carbon nanotube sponge used in the examples.
Fig. 4 is a scanning electron microscope image of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in example 1.
Fig. 5 is a scanning electron micrograph of the silver phosphate photocatalyst prepared in comparative example 1.
Fig. 6 is a scanning electron micrograph of the bismuth oxide photocatalyst prepared in comparative example 2.
Fig. 7 is a graph of the uv-vis diffuse reflectance spectra of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in example 1, the carbon nanotube sponge used in the examples, the silver phosphate photocatalyst prepared in comparative example 1, and the bismuth oxide photocatalyst prepared in comparative example 2, wherein the CNT is a carbon nanotube sponge.
FIG. 8 is a graph showing the degradation performance of the photocatalysts prepared in examples 1 to 3 and comparative examples 1 to 2 with respect to naphthalene.
Fig. 9 is a degradation mechanism diagram of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube composite photocatalyst prepared by the invention.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials and equipment are commercially available, unless otherwise specified.
Carbon nanotube sponges used in the examples were prepared (Gui, X.C., Wei, J.Q., Wang, K.L., Cao, A.Y., Zhu, H.W., Jia, Y., Shu, Q.K., Wu, D.H.Carbon nanotube sponges.advanced materials,2010,22(5): 617. 621.) using dichlorobenzene and ferrocene in a mass ratio of 1:25 at 850 ℃ by chemical vapor deposition, with internal diameters of 20-40nm, and infrared, X-ray and scanning electron micrographs as shown in FIGS. 1-3, respectively.
Example 1
A preparation method of a full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for drilling waste liquid treatment comprises the following steps:
(1) ultrasonically dispersing 1.5g of silver nitrate in 100mL of a mixed solvent of ethanol, ethylene glycol and water, wherein the mass ratio of ethanol: ethylene glycol: obtaining an organic alcohol aqueous solution of silver nitrate according to the volume ratio of water being 1:1:9, then placing 0.3g of carbon nanotube sponge into the organic alcohol aqueous solution of silver nitrate, stirring for 1 hour on a magnetic stirrer at the temperature of 25 ℃ at the stirring speed of 300r/min, so that the silver nitrate is uniformly adsorbed in the porous structure of the carbon nanotube sponge, and obtaining a carbon nanotube sponge/silver nitrate mixed solution; uniformly dispersing 0.5g of disodium hydrogen phosphate in 100mL of water to obtain a disodium hydrogen phosphate solution, dropwise adding the disodium hydrogen phosphate solution into a carbon nano tube sponge/silver nitrate mixed solution within 5min, carrying out hydrothermal reaction at 60 ℃ for 3h, filtering a reaction system under a shading condition after the reaction is finished, washing an obtained product with absolute ethyl alcohol for 3 times under the shading condition, and drying in a vacuum drying oven for 4 hours under the shading condition of 80 ℃ to obtain a silver phosphate/carbon nano tube composite material;
(2) uniformly dispersing 1.4g of sodium bismuthate in 70mL of sodium hydroxide solution with the concentration of 0.5mol/L, stirring for 1 hour at the stirring speed of 300r/min under the condition of shading, then adding 1.4g of the silver phosphate/carbon nanotube composite material obtained in the step (1), then transferring the obtained mixed solution into a reaction kettle with a 100mL Teflon lining, carrying out hydrothermal reaction for 6 hours at 180 ℃, taking out the reaction kettle, cooling to room temperature, filtering under the condition of shading, washing the obtained product for 3 times with deionized water under the condition of shading, and then carrying out freeze drying for 15 hours at-55 ℃ to obtain the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst.
An X-ray diffraction spectrogram of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in the embodiment is shown in fig. 1, and as can be seen from fig. 1, crystal phases of bismuth oxide, silver phosphate and carbon nanotubes can be detected on the composite photocatalyst, which indicates that bismuth oxide and silver phosphate are successfully modified on the carbon nanotubes.
The infrared spectrogram of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in this example is shown in fig. 2, and as can be seen from fig. 2, characteristic adsorption peaks of bismuth oxide, silver phosphate and carbon nanotubes all appear on the spectrogram of the composite photocatalyst, which further proves that bismuth oxide and silver phosphate are modified on the carbon nanotubes.
A scanning electron microscope image of the full-spectrum-response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in the embodiment is shown in fig. 4, and as can be seen from fig. 4, the composite photocatalyst is of a three-dimensional space network structure, and bismuth oxide and silver phosphate are supported on the surface of a carbon nanotube sponge, wherein the bismuth oxide is composed of nanosheets with a thickness of 10-20 nm, and the particle size of the nanosheets is about 6 μm; the particle size of the silver phosphate particles is 200-500 nm; the diameter of the carbon nano tube is 20-40 nm.
An ultraviolet-visible diffuse reflection spectrum diagram of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in the embodiment is shown in fig. 7, and as can be seen from fig. 7, the absorbance of the composite photocatalyst prepared in the embodiment is significantly higher than that of a single bismuth oxide or silver phosphate photocatalyst, and particularly, the composite photocatalyst shows good light response performance in a near-infrared region.
Example 2
A preparation method of a full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for drilling waste liquid treatment comprises the following steps:
(1) ultrasonically dispersing 1.5g of silver nitrate in 100mL of a mixed solvent of ethanol, ethylene glycol and water, wherein the mass ratio of ethanol: ethylene glycol: obtaining an organic alcohol aqueous solution of silver nitrate according to the volume ratio of water being 1:1:9, then placing 0.3g of carbon nanotube sponge into the organic alcohol aqueous solution of silver nitrate, stirring for 1 hour on a magnetic stirrer at the temperature of 25 ℃ at the stirring speed of 300r/min, so that the silver nitrate is uniformly adsorbed in the porous structure of the carbon nanotube sponge, and obtaining a carbon nanotube sponge/silver nitrate mixed solution; uniformly dispersing 0.5g of disodium hydrogen phosphate in 100mL of water to obtain a disodium hydrogen phosphate solution, dropwise adding the disodium hydrogen phosphate solution into a carbon nano tube sponge/silver nitrate mixed solution within 5min, carrying out hydrothermal reaction at 60 ℃ for 3h, filtering a reaction system under a shading condition after the reaction is finished, washing an obtained product with absolute ethyl alcohol for 3 times under the shading condition, and drying in a vacuum drying oven for 4 hours under the shading condition of 80 ℃ to obtain a silver phosphate/carbon nano tube composite material;
(2) uniformly dispersing 4.2g of sodium bismuthate in 70mL of sodium hydroxide solution with the concentration of 0.5mol/L, stirring at the stirring speed of 300r/min for 1 hour under the condition of shading, then adding 1.4g of the silver phosphate/carbon nanotube composite material obtained in the step (1), then transferring the obtained mixed solution into a reaction kettle with a 100mL Teflon lining, carrying out hydrothermal reaction for 6 hours at 180 ℃, taking out the reaction kettle, cooling to room temperature, filtering under the condition of shading, washing the obtained product with deionized water for 3 times under the condition of shading, and then carrying out freeze drying for 15 hours at-55 ℃ to obtain the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst.
The X-ray diffraction spectrum of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in this example is shown in fig. 1.
Example 3
A preparation method of a full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for drilling waste liquid treatment comprises the following steps:
(1) ultrasonically dispersing 1.5g of silver nitrate in 100mL of a mixed solvent of ethanol, ethylene glycol and water, wherein the mass ratio of ethanol: ethylene glycol: obtaining an organic alcohol aqueous solution of silver nitrate according to the volume ratio of water being 1:1:9, then placing 0.3g of carbon nanotube sponge into the organic alcohol aqueous solution of silver nitrate, stirring for 1 hour on a magnetic stirrer at the temperature of 25 ℃ at the stirring speed of 300r/min, so that the silver nitrate is uniformly adsorbed in the porous structure of the carbon nanotube sponge, and obtaining a carbon nanotube sponge/silver nitrate mixed solution; uniformly dispersing 0.5g of disodium hydrogen phosphate in 100mL of water to obtain a disodium hydrogen phosphate solution, dropwise adding the disodium hydrogen phosphate solution into a carbon nano tube sponge/silver nitrate mixed solution within 5min, carrying out hydrothermal reaction at 60 ℃ for 3h, filtering a reaction system under a shading condition after the reaction is finished, washing an obtained product with absolute ethyl alcohol for 3 times under the shading condition, and drying in a vacuum drying oven for 4 hours under the shading condition of 80 ℃ to obtain a silver phosphate/carbon nano tube composite material;
(2) uniformly dispersing 7.0g of sodium bismuthate in 70mL of sodium hydroxide solution with the concentration of 0.5mol/L, stirring for 1 hour at the stirring speed of 300r/min under the condition of shading, then adding 1.4g of the silver phosphate/carbon nanotube composite material obtained in the step (1), then transferring the obtained mixed solution into a reaction kettle with a 100mL Teflon lining, carrying out hydrothermal reaction for 6 hours at 180 ℃, taking out the reaction kettle, cooling to room temperature, filtering under the condition of shading, washing the obtained product for 3 times with deionized water under the condition of shading, and then carrying out freeze drying for 15 hours at-55 ℃ to obtain the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst.
The X-ray diffraction spectrum of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared in this example is shown in fig. 1.
Comparative example 1
A preparation method of a silver phosphate photocatalyst for treating drilling waste liquid comprises the following steps:
ultrasonically dispersing 1.5g of silver nitrate in 100mL of a mixed solvent of ethanol, ethylene glycol and water, wherein the mass ratio of ethanol: ethylene glycol: the volume ratio of water is 1:1:9, and organic alcohol aqueous solution of silver nitrate is obtained; uniformly dispersing 0.5g of disodium hydrogen phosphate in 100mL of water to obtain a disodium hydrogen phosphate solution, dropwise adding the disodium hydrogen phosphate solution into an organic alcohol aqueous solution of silver nitrate within 5min, carrying out hydrothermal reaction on the obtained mixed solution at 60 ℃ for 3h, filtering the reaction system under a shading condition after the reaction is finished, washing the obtained product with absolute ethyl alcohol for 3 times under the shading condition, and drying the reaction product in a vacuum drying oven for 4h under the shading condition of 80 ℃ to obtain the silver phosphate photocatalyst.
The X-ray diffraction spectrum, the scanning electron micrograph and the ultraviolet-visible diffuse reflectance spectrogram of the silver phosphate photocatalyst prepared in the comparative example are respectively shown in fig. 1, 5 and 7.
Comparative example 2
A preparation method of a bismuth oxide photocatalyst for treating drilling waste liquid comprises the following steps:
uniformly dispersing 1.4g of sodium bismuthate in 70mL of 0.5mol/L sodium hydroxide solution, stirring at a stirring speed of 300r/min for 1 hour under a shading condition, then transferring the obtained mixed solution into a reaction kettle with a 100mL Teflon lining, carrying out hydrothermal reaction at 180 ℃ for 6 hours, taking out the reaction kettle, cooling to room temperature, filtering under the shading condition, washing with deionized water for 3 times under the shading condition, and carrying out vacuum drying at 80 ℃ for 6 hours to obtain the bismuth oxide photocatalyst.
The X-ray diffraction spectrum, the scanning electron microscope image and the ultraviolet-visible diffuse reflectance spectrum of the bismuth oxide photocatalyst prepared in the comparative example are respectively shown in fig. 1, fig. 6 and fig. 7.
Test example 1
The photocatalysts prepared in the examples 1-3 and the comparative examples 1-2 are subjected to a photodegradation experiment of polycyclic aromatic hydrocarbons in drilling waste liquid, 100mg of the prepared photocatalyst is placed in 100mL of 5mg/L naphthalene solution, and the light is shielded for 30min to reach adsorption balance. Then, a light reaction was performed using a 300W xenon lamp light source with a filter (wavelength >420nm), 5mL of a sample of the solution was sampled at regular intervals to measure the concentration, and the concentration of naphthalene in the solution was measured using a fluorescence spectrophotometer.
The degradation performance curves of the photocatalysts prepared in examples 1-3 and comparative examples 1-2 on naphthalene are shown in fig. 8, and the naphthalene concentration in the solution after the start of the photoreaction is significantly reduced with the increase of the photoreaction time. After 20min of reaction, the degradation rates of the photocatalysts prepared in examples 1 to 3 on naphthalene reach 89.3%, 92.5% and 90.1% respectively, while the degradation rates of the photocatalysts prepared in comparative examples 1 and 2 on naphthalene reach 83.8% and 87.5% respectively, which shows that the composite catalyst prepared by the invention can remove most of naphthalene in a short time and has good photocatalytic activity.
Test example 2
The photocatalysts prepared in the examples 2-3 and the comparative examples 1-2 are subjected to a photodegradation experiment of polycyclic aromatic hydrocarbons in drilling waste liquid, 100mg of the prepared photocatalyst is placed in 100mL of pyrene solution with the concentration of 5mg/L, and the light is shielded for 30min to achieve adsorption balance. Performing light reaction (wavelength is more than 420nm) by using a 300W xenon lamp light source with a filter, taking 5mL of solution samples at regular intervals, measuring the concentration, and detecting the concentration of pyrene in the solution by using a fluorescence spectrophotometer.
After the photoreaction is carried out for 10min, the degradation rates of the photocatalysts prepared in the examples 2 and 3 to pyrene can reach 80.3% and 74.0% respectively, while the degradation rates of the photocatalysts prepared in the comparative examples 1-2 to pyrene are 65%, which shows that the composite catalyst prepared by the invention has good photodegradation performance to pyrene.
The degradation mechanism of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst prepared by the invention is shown in fig. 9, bismuth oxide and silver phosphate can form a heterostructure, photoproduction electrons and holes are generated under the irradiation of visible light or near infrared light, the excellent conductivity and the three-dimensional space structure of the carbon nanotube sponge can effectively improve the transfer efficiency of the photoproduction electrons, and the electron-hole recombination is avoided, so that the aim of improving the photocatalytic activity is fulfilled.
Claims (12)
1. The full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for drilling waste liquid treatment is characterized by being formed by self-assembling silver phosphate, bismuth oxide and carbon nanotube sponge, wherein the silver phosphate and the bismuth oxide are loaded on the carbon nanotube sponge;
the preparation method comprises the following steps:
(1) adding carbon nanotube sponge into silver nitrate organic alcohol aqueous solution, stirring, then adding disodium hydrogen phosphate solution, and carrying out hydrothermal reaction on the obtained mixed solution; filtering, washing and drying to obtain the silver phosphate/carbon nano tube sponge composite material;
(2) adding sodium bismuthate into a sodium hydroxide solution, stirring, adding the silver phosphate/carbon nano tube sponge composite material obtained in the step (1), and carrying out hydrothermal reaction on the obtained mixed solution; filtering, washing, freezing and drying to obtain a full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst; the mass ratio of the sodium hydroxide to the sodium bismuthate is 1: 1-5.
2. The full-spectrum-response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst as claimed in claim 1, wherein the silver phosphate has a particle size of 200-500 nm; the bismuth oxide is micron particles composed of nanosheets with the thickness of 10-20 nm, and the particle size of the particles is 2-6 microns; the pore diameter of the carbon nanotube sponge is 0.5-2.0 mu m, the inner diameter of the carbon nanotube in the carbon nanotube sponge is 20-40nm, and the thickness of the tube wall is 5-20 nm.
3. The full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst as claimed in claim 1, wherein the mass ratio of the carbon nanotube sponge to the silver nitrate in step (1) is 1: 5-15.
4. The full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst as claimed in claim 1, wherein the mass concentration of silver nitrate in the silver nitrate organic alcohol aqueous solution in the step (1) is 0.01-0.015 g/mL;
the preparation method of the silver nitrate organic alcohol aqueous solution comprises the following steps: ultrasonically dispersing silver nitrate into a mixed solvent of organic alcohol and water; the organic alcohol is one or the combination of two of methanol, ethanol, glycol, propanol and n-butanol; the volume ratio of the organic alcohol to the water is 1: 4-10.
5. The full-spectrum-response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst as claimed in claim 4, wherein the organic alcohol is one or a combination of methanol, ethanol and ethylene glycol.
6. The full-spectrum-response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst as claimed in claim 5, wherein the organic alcohol is one or a combination of ethanol and ethylene glycol.
7. The full-spectrum-response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst as claimed in claim 6, wherein the organic alcohol is a combination of ethanol and ethylene glycol, and the volume ratio of ethanol to ethylene glycol is 1: 1.
8. The full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst as claimed in claim 1, wherein the mass concentration of the disodium hydrogen phosphate solution in the step (1) is 0.005-0.01 g/mL; the mass ratio of the disodium hydrogen phosphate to the silver nitrate is 1: 1-10.
9. The full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst as claimed in claim 1, wherein the stirring conditions in step (1) are as follows: the stirring temperature is 20-25 ℃, the stirring speed is 200-500 r/min, and the stirring time is 0.5-2 h;
the temperature of the hydrothermal reaction is 50-70 ℃, and the time of the hydrothermal reaction is 2-4 h;
the filtering, washing and drying are carried out under the shading condition, the washing is carried out for 3 times by using absolute ethyl alcohol, and the drying is carried out for 3-5 hours in vacuum at the temperature of 70-90 ℃.
10. The full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst of claim 1, wherein step (2) comprises one or more of the following conditions:
(a) the concentration of the sodium hydroxide solution is 0.3-0.7 mol/L, and the mass ratio of sodium hydroxide to sodium bismuthate is 1: 2-4; the stirring is carried out under the shading condition;
(b) the mass ratio of the silver phosphate/carbon nano tube sponge composite material to the sodium bismuthate is 1: 1-5;
(c) the conditions of the hydrothermal reaction are as follows: the temperature is 150-250 ℃, and the reaction time is 5-8 hours;
(d) the filtration, washing and freeze drying are carried out under the shading condition; the washing is carried out for three times by using deionized water; the freeze drying is drying at-50 to-60 ℃ for 12 to 24 hours.
11. The use of the full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst as defined in any one of claims 1 to 10, as a photocatalyst for degrading polycyclic aromatic hydrocarbons in drilling fluid under irradiation conditions of visible light and near infrared light.
12. The use according to claim 11, wherein the polycyclic aromatic hydrocarbon is one or a combination of at least two of naphthalene, phenanthrene and pyrene.
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