CN112264058A - Fe and P co-doped strontium titanate/rectorite composite catalyst and application thereof - Google Patents
Fe and P co-doped strontium titanate/rectorite composite catalyst and application thereof Download PDFInfo
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 9
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Images
Classifications
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- B01J35/33—
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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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
Abstract
The invention discloses a Fe and P co-doped strontium titanate/rectorite composite catalyst and application thereof, wherein the composite catalyst is formed by compounding natural clay mineral rectorite serving as a carrier with Fe and P co-doped strontium titanate; the composite catalyst can effectively degrade organic pollutants in a visible light range under the radiation of sunlight in the treatment of the organic pollutants, and then is separated from a solution after reaction through a magnetic carrying effect and is repeatedly used. The composite catalyst of the invention forms a pillared composite material to expand an interlayer domain by inserting semiconductor nano particles with smaller particle size such as doped and modified nano strontium titanate into rectorite, the expanded interlayer domain has high structural stability, inhibits the growth of nano particles, plays a role in promoting the separation of photogenerated electrons and cavities, and simultaneously can improve the specific surface area and pore volume of the composite material, enhance the adsorption performance and effectively remove organic pollutants in industrial wastewater.
Description
Technical Field
The invention relates to the field of environment-friendly materials, in particular to a Fe and P co-doped strontium titanate/rectorite composite catalyst and application thereof.
Background
The organic pollutants refer to pollutants composed of natural organic substances existing in the forms of carbohydrates, proteins, amino acids, fats and the like and some other biodegradable artificially synthesized organic substances. Can be divided into two categories of natural organic pollutants and artificially synthesized organic pollutants. The water contains a large amount of organic pollutants which affect the ecosystem in the form of toxicity and reduction of dissolved oxygen in water, and are harmful to human health.
Strontium titanate has the advantages of stable chemical structure, environmental friendliness, capability of realizing photocatalysis under unbiased pressure and the like, is widely applied to the fields of environmental management and clean energy development, and is a potential semiconductor catalytic material. Strontium titanate has the characteristics of high forbidden band width, excellent photocatalytic activity and the like, has unique electromagnetic property and redox catalytic activity, and is widely applied to the photocatalytic fields of photocatalytic water splitting hydrogen production, photocatalytic organic pollutant degradation, photochemical batteries and the like, but has the problems of poor dispersibility in solution degradation, difficult separation and recovery after use, secondary pollution and the like due to the fact that strontium titanate oxide has wide band gap, low quantum efficiency and light irradiation response only in the ultraviolet light range, and the practical application of strontium titanate oxide in industry is limited. Therefore, there is a need to modify strontium titanate to expand the application of strontium titanate in the treatment of organic contaminants.
Disclosure of Invention
In order to solve the above-mentioned drawbacks in the background art, the present invention provides a Fe and P co-doped strontium titanate/rectorite composite catalyst, which is formed by compounding natural clay mineral rectorite as a carrier with Fe and P co-doped strontium titanate, and a pillared composite material is formed by inserting semiconductor nanoparticles with small particle size, such as doped and modified nano strontium titanate, into the rectorite to expand an interlayer domain, so that the stability of the expanded interlayer domain structure can be greatly improved, the growth of the nanoparticles can be inhibited, the separation of photo-generated electrons and holes can be promoted, and meanwhile, the specific surface area and pore volume of the composite material can be improved, the adsorption performance can be enhanced, and organic pollutants in industrial wastewater can be effectively removed.
The purpose of the invention can be realized by the following technical scheme:
the composite catalyst is formed by compounding natural clay mineral rectorite serving as a carrier with Fe and P co-doped strontium titanate, and specifically comprises the following steps:
(1) weighing strontium nitrate, dissolving the strontium nitrate in deionized water, stirring, adding citric acid serving as a complexing agent, uniformly stirring until the strontium nitrate is completely dissolved to obtain a transparent solution A, dissolving tetrabutyl titanate in ethylene glycol to obtain a solution B, weighing ferric nitrate nonahydrate and disodium hydrogen phosphate, and dissolving the ferric nitrate nonahydrate and the disodium hydrogen phosphate in the ethylene glycol to obtain a solution C;
(2) slowly dripping the solution C into the solution B at the speed of 2-3 drops per second under magnetic stirring, stirring for 10-15min to obtain a solution D, then slowly dripping the solution A into the solution D, and continuously stirring until gel is formed;
(3) adding pretreated rectorite with the mass being 20-40% of that of the gel into the gel, heating and stirring for 10-15min, carrying out centrifugal separation at the rotating speed of 3000r/min for 2000-plus-material, then drying at 120 ℃ in a drying box, grinding, then putting into a muffle furnace for calcining, heating to 200-plus-material temperature and keeping the temperature for 2-3h at 300 ℃, heating to 500-plus-material temperature and keeping the temperature for 1-2h at 600 ℃, then heating to 700-plus-material temperature and keeping the temperature for 0.5-1h at 800 ℃, naturally cooling and then taking out to obtain the Fe-P co-doped strontium titanate/rectorite composite catalyst.
Preferably, the mass ratio of the strontium nitrate to the citric acid in the step (1) is 1: 3-4.
Preferably, the volume ratio of tetrabutyl titanate to ethylene glycol in step (1) is 1: 3-4.
Preferably, the molar ratio of ferric nitrate nonahydrate to disodium hydrogen phosphate in step (1) is 1: 1.
Preferably, the rectorite pretreatment method in the step (3) is as follows: grinding rectorite to be below 100 meshes, adding rectorite into distilled water according to a solid-liquid ratio of 1:6-8, heating and stirring in a water bath at 70-80 ℃ to prepare slurry, then adding hexadecyl trimethyl ammonium bromide which accounts for 5-10% of the mass of the rectorite, ball-milling for 20-30min, performing ultrasonic dispersion for 40-50min, performing low-speed centrifugal separation to remove impurities, pouring out the rest suspension, performing high-speed centrifugal separation, washing, drying and grinding the bottom substance to obtain the pretreated crosslinked rectorite.
Preferably, the rotation speed in the low-speed centrifugal separation is 600-800r/min, and the centrifugation time is 30-40 min.
Preferably, the rotating speed in the high-speed centrifugal separation is 6000-.
The composite catalyst can effectively degrade organic pollutants in a visible light range under the radiation of sunlight, and then is separated from a solution after reaction through a magnetic loading effect and is repeatedly used.
The invention has the beneficial effects that:
according to the invention, the charge compensation co-doping of the magnetic metal Fe and the nonmetal P can effectively reduce the band gap, expand the light absorption range and have high catalytic activity. The rectorite layer has good cation exchange performance and dispersibility and strong adsorption capacity, and the particle size of the co-doped strontium titanate catalyst can be effectively reduced and the dispersibility of the catalyst can be improved by pre-treating and then loading rectorite minerals. The doped and modified strontium titanate and the pretreated rectorite are compounded to generate a synergistic effect by combining the two, narrow-band-gap photocatalytic particles loaded on the surface of the rectorite generate photoproduction electron hole pairs under the irradiation of ultraviolet light, because the rectorite has stronger adsorbability between layers, a sufficient adsorption surface is provided for reactants, and the adsorbed organic matters can more easily obtain free active groups by the stronger surface activity, so that the photocatalytic activity can be obviously enhanced.
According to the invention, a concept of co-doping magneto-optical regulation and mineral loading is adopted, and a sol-gel method is adopted to prepare the Fe and P co-doping strontium titanate/rectorite composite catalyst, so that the composite catalyst has good light stability, has a good removal effect on organic matters in sewage under visible light, and has high catalytic activity; the catalyst has good adsorption capacity, the rectorite carrier subjected to crosslinking treatment has good dispersibility, the photocatalytic reaction rate and efficiency can be increased, and organic pollutants in sewage can be efficiently and quickly adsorbed and degraded; the magnetic supported catalyst has good crystallinity and high purity, and realizes magnetic separation, recovery and cyclic utilization.
Drawings
FIG. 1 shows the solid UV-Vis diffuse reflectance spectrum of the Fe and P co-doped strontium titanate/rectorite composite catalyst prepared in example 1 of the present invention;
fig. 2 shows the results of nitrogen adsorption-desorption tests of Fe, P co-doped strontium titanate/rectorite catalyst prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "opening," "upper," "lower," "thickness," "top," "middle," "length," "inner," "peripheral," and the like are used in an orientation or positional relationship that is merely for convenience in describing and simplifying the description, and do not indicate or imply that the referenced component or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be considered as limiting the present invention.
Example 1
The composite catalyst is formed by compounding natural clay mineral rectorite serving as a carrier with Fe and P co-doped strontium titanate, and specifically comprises the following steps:
(1) weighing 2.12g of strontium nitrate, dissolving the strontium nitrate in 30mL of deionized water, stirring, adding 5.77g of citric acid serving as a complexing agent, uniformly stirring until the strontium nitrate is completely dissolved to obtain a transparent solution A, dissolving 2.66mL of tetrabutyl titanate in 8.0mL of ethylene glycol to obtain a solution B, weighing 0.51g of ferric nitrate nonahydrate and 0.18g of disodium hydrogen phosphate, and dissolving in 5mL of ethylene glycol to obtain a solution C;
(2) slowly dripping the solution C into the solution B at the speed of 2-3 drops per second under magnetic stirring, stirring for 10min to obtain a solution D, then slowly dripping the solution A into the solution D, and continuously stirring until gel is formed;
(3) adding pretreated rectorite which accounts for 20% of the mass of the gel into the gel, heating and stirring for 15min, centrifugally separating at the rotating speed of 2000r/min, drying at 100 ℃ in a drying box, grinding, calcining in a muffle furnace, heating to 200 ℃, keeping the temperature for 3h, heating to 500 ℃, keeping the temperature for 2h, heating to 700 ℃, keeping the temperature for 1h, naturally cooling, and taking out to obtain the Fe and P co-doped strontium titanate/rectorite composite catalyst.
The method for pretreating rectorite in the step (3) comprises the following steps: grinding rectorite to be below 100 meshes, adding rectorite into distilled water according to a solid-liquid ratio of 1:6, heating and stirring the mixture in a water bath at 70 ℃ to prepare slurry, obtaining rectorite suspension, adding hexadecyl trimethyl ammonium bromide which accounts for 5 percent of the mass of the rectorite, ball-milling the mixture for 20min, performing ultrasonic dispersion for 40min, performing low-speed centrifugal separation to remove impurities, pouring out the rest suspension, performing high-speed centrifugal separation, and washing, drying and grinding a bottom substance to obtain the pretreated crosslinked rectorite.
Example 2
The composite catalyst is formed by compounding natural clay mineral rectorite serving as a carrier with Fe and P co-doped strontium titanate, and specifically comprises the following steps:
(1) weighing 2.12g of strontium nitrate, dissolving the strontium nitrate in 30mL of deionized water, stirring, adding 6.76g of citric acid serving as a complexing agent, uniformly stirring until the strontium nitrate is completely dissolved to obtain a transparent solution A, dissolving 2.66mL of tetrabutyl titanate in 8.0mL of ethylene glycol to obtain a solution B, weighing 0.51g of ferric nitrate nonahydrate and 0.18g of disodium hydrogen phosphate, and dissolving in 5mL of ethylene glycol to obtain a solution C;
(2) slowly dripping the solution C into the solution B at the speed of 2-3 drops per second under magnetic stirring, stirring for 10min to obtain a solution D, then slowly dripping the solution A into the solution D, and continuously stirring until gel is formed;
(3) adding pretreated rectorite with the mass equivalent to 30% of that of the gel into the gel, heating and stirring for 15min, centrifugally separating at the rotating speed of 2500r/min, drying at 110 ℃ in a drying box, grinding, calcining in a muffle furnace, heating to 250 ℃, keeping the temperature for 2h, heating to 550 ℃, keeping the temperature for 1.5h, heating to 750 ℃, keeping the temperature for 1h, naturally cooling, and taking out to obtain the Fe and P co-doped strontium titanate/rectorite composite catalyst.
The rectorite pretreatment method in the step (3) is as follows: grinding rectorite to be below 100 meshes, adding rectorite into distilled water according to a solid-liquid ratio of 1:7, heating and stirring the rectorite in a water bath at 75 ℃ to prepare slurry, obtaining rectorite suspension, adding hexadecyl trimethyl ammonium bromide which accounts for 7.5 percent of the mass of the rectorite, ball-milling the mixture for 25min, performing ultrasonic dispersion for 45min, performing low-speed centrifugal separation to remove impurities, pouring out the rest suspension, performing high-speed centrifugal separation, and washing, drying and grinding a bottom substance to obtain the pretreated crosslinked rectorite.
Example 3
The composite catalyst is formed by compounding natural clay mineral rectorite serving as a carrier with Fe and P co-doped strontium titanate, and specifically comprises the following steps:
(1) weighing 2.12g of strontium nitrate, dissolving the strontium nitrate in 30mL of deionized water, stirring, adding 7.73g of citric acid serving as a complexing agent, uniformly stirring until the citric acid is completely dissolved to obtain a transparent solution A, dissolving 2.66mL of tetrabutyl titanate in 8.0mL of ethylene glycol to obtain a solution B, weighing 0.51g of ferric nitrate nonahydrate and 0.18g of disodium hydrogen phosphate, and dissolving in 5mL of ethylene glycol to obtain a solution C;
(2) slowly dripping the solution C into the solution B at the speed of 2-3 drops per second under magnetic stirring, stirring for 10min to obtain a solution D, then slowly dripping the solution A into the solution D, and continuously stirring until gel is formed;
(3) adding pretreated rectorite which accounts for 40% of the mass of the gel into the gel, heating and stirring for 15min, centrifugally separating at the rotating speed of 3000r/min, drying at 120 ℃ in a drying box, grinding, calcining in a muffle furnace, heating to 250 ℃, keeping the temperature for 2h, heating to 550 ℃, keeping the temperature for 1.5h, heating to 750 ℃, keeping the temperature for 0.5h, naturally cooling, and taking out to obtain the Fe and P co-doped strontium titanate/rectorite composite catalyst.
The rectorite pretreatment method in the step (3) is as follows: grinding rectorite to be below 100 meshes, adding rectorite into distilled water according to a solid-liquid ratio of 1:8, heating and stirring the mixture in a water bath at 80 ℃ to prepare slurry, obtaining rectorite suspension, adding hexadecyl trimethyl ammonium bromide accounting for 10% of the mass of the rectorite to perform ball milling for 30min, performing ultrasonic dispersion for 50min, performing low-speed centrifugal separation to remove impurities, pouring out the rest suspension, performing high-speed centrifugal separation, and washing, drying and grinding a bottom substance to obtain the pretreated crosslinked rectorite.
Performance detection
1. Two samples of the Fe and P co-doped strontium titanate/rectorite composite catalyst prepared in example 1 were subjected to a solid uv-vis diffuse reflection test and a BET specific surface area test (nitrogen adsorption-desorption), respectively, and the results obtained are shown in fig. 1-2.
The ultraviolet-visible absorption spectrum given in FIG. 1 shows that the supported catalytic material has strong visible light absorption capacity; as can be seen from the results of the nitrogen adsorption-desorption test in FIG. 2, the prepared sample has a typical microporous and mesoporous porous channel structure, and the specific surface area of the sample is 42.9m2The concentration of the catalyst is about 3 times of that of rectorite, and the catalyst is favorable for enhancing the adsorption of the catalyst on pollutants, thereby improving the photocatalytic degradation effect.
2. The Fe and P co-doped strontium titanate/rectorite composite catalyst synthesized by the method is used for degrading methyl orange solution, and the specific reaction conditions are as follows: and (3) taking a xenon lamp as a light source, adding a filter plate between the light source and the degradation solution to remove ultraviolet light, stirring at room temperature for 30 minutes to ensure that the solution reaches adsorption balance, then sampling the test solution once every 15 minutes of irradiation, and taking the supernatant after centrifugal separation for absorbance test. After magnetic separation, the catalyst can be recycled for 5 times.
The result shows that 20ppm of methyl orange solution can be completely degraded in 60 minutes under the irradiation of visible light, and further shows that the composite catalyst can enhance the photocatalytic reaction rate and efficiency, and can efficiently and rapidly adsorb and degrade organic matters in water.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (8)
1. The Fe and P co-doped strontium titanate/rectorite composite catalyst is characterized in that the composite catalyst is formed by compounding natural clay mineral rectorite serving as a carrier with Fe and P co-doped strontium titanate, and specifically comprises the following steps:
(1) weighing strontium nitrate, dissolving the strontium nitrate in deionized water, stirring, adding citric acid serving as a complexing agent, uniformly stirring until the strontium nitrate is completely dissolved to obtain a transparent solution A, dissolving tetrabutyl titanate in ethylene glycol to obtain a solution B, weighing ferric nitrate nonahydrate and disodium hydrogen phosphate, and dissolving the ferric nitrate nonahydrate and the disodium hydrogen phosphate in the ethylene glycol to obtain a solution C;
(2) slowly dripping the solution C into the solution B at the speed of 2-3 drops per second under magnetic stirring, stirring for 10-15min to obtain a solution D, then slowly dripping the solution A into the solution D, and continuously stirring until gel is formed;
(3) adding pretreated rectorite with the mass being 20-40% of that of the gel into the gel, heating and stirring for 10-15min, carrying out centrifugal separation at the rotating speed of 3000r/min for 2000-plus-material, then drying at 120 ℃ in a drying box, grinding, then putting into a muffle furnace for calcining, heating to 200-plus-material temperature and keeping the temperature for 2-3h at 300 ℃, heating to 500-plus-material temperature and keeping the temperature for 1-2h at 600 ℃, then heating to 700-plus-material temperature and keeping the temperature for 0.5-1h at 800 ℃, naturally cooling and then taking out to obtain the Fe-P co-doped strontium titanate/rectorite composite catalyst.
2. The Fe and P co-doped strontium titanate/rectorite composite catalyst as claimed in claim 1, wherein the mass ratio of strontium nitrate and citric acid in the step (1) is 1: 3-4.
3. The Fe and P co-doped strontium titanate/rectorite composite catalyst according to claim 1, wherein the volume ratio of tetrabutyl titanate and ethylene glycol in the step (1) is 1: 3-4.
4. The Fe and P co-doped strontium titanate/rectorite composite catalyst according to claim 1, wherein the molar ratio of ferric nitrate nonahydrate to disodium hydrogen phosphate in step (1) is 1: 1.
5. The Fe and P co-doped strontium titanate/rectorite composite catalyst according to claim 1, wherein the rectorite pretreatment method in the step (3) is as follows: grinding rectorite to be below 100 meshes, adding rectorite into distilled water according to a solid-liquid ratio of 1:6-8, heating and stirring in a water bath at 70-80 ℃ to prepare slurry, then adding hexadecyl trimethyl ammonium bromide which accounts for 5-10% of the mass of the rectorite, ball-milling for 20-30min, performing ultrasonic dispersion for 40-50min, performing low-speed centrifugal separation to remove impurities, pouring out the rest suspension, performing high-speed centrifugal separation, washing, drying and grinding the bottom substance to obtain the pretreated crosslinked rectorite.
6. The Fe and P co-doped strontium titanate/rectorite composite catalyst as claimed in claim 5, wherein the rotation speed in the low-speed centrifugal separation is 600-800r/min, and the centrifugation time is 30-40 min.
7. The Fe and P co-doped strontium titanate/rectorite composite catalyst as claimed in claim 5, wherein the rotation speed in the high-speed centrifugal separation is 6000-8000r/min, and the centrifugation time is 10-20 min.
8. Use of the Fe, P co-doped strontium titanate/rectorite composite catalyst according to any one of claims 1 to 7 in the treatment of organic pollutants, wherein the composite catalyst can effectively degrade organic pollutants in the visible light range under solar radiation, and then is separated from the reacted solution by magnetic loading and reused.
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