CN115582130B - Preparation method of photo-Fenton catalyst and application of photo-Fenton catalyst in organic wastewater treatment - Google Patents
Preparation method of photo-Fenton catalyst and application of photo-Fenton catalyst in organic wastewater treatment Download PDFInfo
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- 239000002071 nanotube Substances 0.000 claims abstract description 42
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 32
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- 238000000034 method Methods 0.000 claims description 42
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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Abstract
The invention belongs to the technical field of catalytic materials, and discloses a preparation method and application of a photo-Fenton catalyst. The preparation method comprises the following steps: adding halloysite nanotubes into sulfuric acid and nitric acid for pretreatment; dissolving bismuth nitrate and ferric nitrate in dilute nitric acid, adding glycine, and dropwise adding ammonia water until the pH of the solution is 7 to 10 to obtain a precursor solution; mixing the precursor solution with the pretreated halloysite nanotube, and heating until the water content of the solution is evaporated to dryness to form gel; and (3) placing the gel in a furnace, setting the furnace temperature to enable the gel to generate spontaneous combustion, then cooling to room temperature, and grinding to obtain the photo-Fenton catalyst. The photo-Fenton catalyst is compounded with the bismuth ferrite, so that the photo-Fenton catalyst has a good photo-catalysis effect, a wide pH application range, a good effect of degrading organic wastewater by UV Fenton and a high degradation rate; the synthesis cost is low, the environment is friendly, and the synthesis and preparation are simple; is favorable for recovery and separation and can be repeatedly recycled.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, relates to a preparation method and application of a photo-Fenton catalyst, and more particularly relates to a preparation method and application of a photo-Fenton catalyst suitable for UV Fenton degradation of organic wastewater.
Background
In recent years, with the rapid development of industrialization, a large amount of organic wastewater (such as dye, pharmacy, chemical industry and the like) is discharged to a water environment, and the wastewater has the characteristics of complex organic matter components, high chromaticity, poor biodegradability and the like, so that the water pollution condition is increasingly serious, the treatment difficulty is increased, and the ecological balance and ecological balance are seriously threatenedIn order to deal with the harm of organic wastewater, many scholars at home and abroad strive to develop various methods for degrading organic wastewater. The Fenton method has the advantages of low reaction condition, low energy consumption, simple operation and the like, overcomes the problems of the traditional organic wastewater treatment method, and draws wide attention of researchers at home and abroad, but the homogeneous Fenton reaction has the defects of large amount of iron mud, narrow pH application range, fe generation 2+ Slow regeneration step, H 2 O 2 The low utilization rate of the catalyst limits the wide application of the catalyst.
The photo-Fenton technology takes light as an energy source to be introduced into a Fenton system, so that the yield of hydroxyl radicals, the mineralization degree of organic matters and the cycle efficiency of iron in the traditional Fenton system are improved, and the photo-Fenton technology receives wide attention. However, at present, the Fenton system is still limited by a plurality of factors on the way of practical application, the pH application range of the Fenton material is narrow, and H is 2 O 2 The utilization rate of the waste water is not high, the cost is high, the recycling is difficult after the waste water is used, and the like.
Bismuth ferrite (BiFeO) 3 ) The bismuth perovskite material has low toxicity and low cost, has narrow forbidden band width (2.0-2.6 eV), wide spectral response range, good photocatalytic activity under ultraviolet and visible light irradiation, good stability under acidic conditions, ferromagnetism and convenient recycling, and is a photocatalyst with great application prospect in the field of photodegradation of organic matters in recent years. However, the photocatalyst still has the problems of few reactive sites on the surface of the material, low light absorption rate and quantum efficiency, and fast recombination of photo-generated electron/hole pairs, and needs to be improved.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a method for preparing a photo-fenton catalyst, wherein the photo-fenton catalyst prepared by the method has a good photo-catalytic effect, is beneficial to recovery and separation, and can be recycled.
The second purpose of the invention is to provide an application of the photo-Fenton catalyst.
In order to realize the purpose of the invention, the specific technical scheme is as follows:
a preparation method of a photo-Fenton catalyst for degrading methyl green comprises the following steps:
(1) Adding a halloysite nanotube into a mixed acid solution of sulfuric acid and nitric acid, performing ultrasonic treatment at the temperature of 60-80 ℃ for 4-6 h, cleaning, drying and grinding the obtained product to obtain a pretreated halloysite nanotube;
(2) Dissolving bismuth nitrate and ferric nitrate in dilute nitric acid, uniformly mixing, adding glycine, and then dropwise adding ammonia water until the pH value of the solution is 7 to 10 to obtain a precursor solution;
(3) Mixing the precursor solution obtained in the step (2) with the pretreated halloysite nanotube obtained in the step (1) for ultrasonic dispersion, and heating until the water in the solution is evaporated to dryness to form gel;
(4) Placing the gel obtained in the step (3) in a furnace, setting the furnace temperature to enable the gel to generate spontaneous combustion, then cooling to room temperature, and grinding to obtain BiFeO 3 @ halloysite nanotube photo-fenton catalyst.
Preferably, in the step (1), the concentration of the sulfuric acid is 3 to 5mol/L, and the concentration of the nitric acid is 3 to 5mol/L; the volume ratio of the sulfuric acid to the nitric acid is 1:3~1:5; the liquid-solid ratio of the nitric acid to the halloysite nanotube is 10 to 15mL/g.
Preferably, in the step (1), the washing specifically comprises: and alternately cleaning the mixture to be neutral by using deionized water and ethanol.
Preferably, in the step (2), the concentration of the dilute nitric acid is 2 to 3mol/L; the bismuth nitrate: iron nitrate: the dosage ratio of the dilute nitric acid is 0.001 to 0.005mol:0.001 to 0.005mol:100mL, wherein the ratio of bismuth nitrate: the molar ratio of ferric nitrate is 1:1.
preferably, in the step (2), the molar ratio of glycine to bismuth nitrate is 1:1~2:1.
preferably, in the step (3), the solid-to-liquid ratio of the pretreated halloysite nanotube to the precursor solution is 2 to 3g/100 mL, and the heating temperature is 60 to 90 ℃.
Preferably, in the step (4), the furnace temperature is set to be 250 to 450 ℃, and the gel is spontaneously combusted.
The invention also discloses an application of the photo-Fenton catalyst prepared by the preparation method in the UV Fenton wastewater treatment process, which comprises the following steps:
step S1, placing organic wastewater in a reaction container, and adjusting the pH to 3 to 11;
step S2, adding hydrogen peroxide, a photo-Fenton catalyst and oxalic acid into a reaction container;
and S3, carrying out UV Fenton degradation reaction under the irradiation of ultraviolet light.
Preferably, in the step S1, the organic matter in the organic wastewater includes methyl green, and the mass concentration of the methyl green is 100 to 200mg/L.
Preferably, in step S1, the pH is adjusted to 3 to 11 with 2 to 3mol/L sulfuric acid solution and 2 to 3mol/L sodium hydroxide solution.
Preferably, in step S2, 0.1 to 0.4g of photo-Fenton catalyst, 5 to 20mmol of hydrogen peroxide, and 0 to 0.1g of sodium oxalate or oxalic acid are added to 1L of organic wastewater.
Preferably, in the step S3, a low-pressure mercury lamp is adopted, the illumination time is 1 to 4 hours, and the reaction temperature is 20 to 25 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) The photo-Fenton catalyst is compounded with the bismuth ferrite, so that the photo-Fenton catalyst has a good photo-catalysis effect, a wide pH application range, a good UV Fenton organic wastewater degradation effect and a high degradation rate; the synthesis cost is low, the environment is friendly, and the synthesis and preparation are simple; is favorable for recovery and separation and can be repeatedly recycled.
(2) The photo-Fenton catalyst is compounded with Halloysite Nanotubes (HNTs), the HNTs have large specific surface area, unique tubular structure and rich pore canals, the outer surface of the HNTs contains a small amount of hydroxyl, and the HNTs have better dispersibility and potential hydrogen bond forming capability compared with other clay minerals. The HNTs are used as a carrier of the photocatalyst, so that the agglomeration of the photocatalyst can be prevented, the active sites are increased, and the photo-Fenton catalyst is convenient to recycle; the existence of a large amount of hydroxyl in the ore can also form stable chemical bonds with the semiconductor, the formation of the chemical bonds enhances the connection between the two, and the separation of photo-generated charges is further accelerated, so that the photocatalytic activity is improved. In addition, light irradiates on the halloysite composite material, and a hollow pipe cavity of the halloysite composite material can reflect light for multiple times, so that the utilization rate of the catalyst to the light is effectively increased.
(3) The ultraviolet Fenton degradation system of the invention introduces oxalic acid which has sensitization effect on photo-oxidation, carboxylic acid and Fe (III) can form complexes with high optical activity, and the complexes generate a series of photochemical reactions under the illumination condition to generate a series of free radicals with strong redox capability, thereby further strengthening the reduction of iron ions in the system. In addition, the carboxylic acid and Fe (III) can form a complex with a large stability coefficient, so that the pH application range of the system is further expanded.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows the difference Bi (NO) in example 1~5 3 ) 3 ·5H 2 O and Fe (NO) 3 ) 3 ·9H 2 And (3) preparing an activity test chart for degrading methyl green by using the ultraviolet Fenton catalytic formula according to the content of O.
FIG. 2 is a graph of methyl green degradation activity of UV-like Fenton catalytic formulations prepared at different synthetic pH's in example 7~9.
FIG. 3 is a graph showing the methyl green degradation activity of UV Fenton-like catalytic formulations prepared according to different glycine dosages in examples 11 to 15.
FIG. 4 is a graph showing methyl green degradation activity of UV Fenton-like catalytic formulations prepared in examples 17 to 19 under different water bath temperatures.
FIG. 5 is a test chart of methyl green degradation activity of the UV Fenton catalytic formulation prepared at different ignition temperatures in examples 21 to 23.
FIG. 6 is a graph showing the activity of the photo-Fenton catalysts in examples 25 to 27 in degrading methyl green at different catalyst dosages.
FIG. 7 is a graph showing the methyl green degradation activity of the photo-Fenton catalysts in examples 28 to 31 under different hydrogen peroxide concentrations.
FIG. 8 is a graph showing the degradation activity of the photo-Fenton catalysts in examples 32 to 37 under different oxalic acid addition amounts.
FIG. 9 is a graph showing the test results of the activity of the photo-Fenton catalysts in examples 38 to 42 for degrading methyl green at different pH values.
FIG. 10 is a graph showing the effect of the photo-Fenton catalyst on the recycling of methyl green in example 43.
Detailed Description
In order to facilitate an understanding of the invention, reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings, and the scope of the invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The present example provides a method for preparing a photo-fenton catalyst, specifically comprising the following steps:
(1) Drying 10g of halloysite nanotubes, adding 5M 20mL sulfuric acid and 5M 100mL nitric acid, performing ultrasonic treatment for 5 hours at the temperature of 70 ℃, alternately cleaning the obtained product to be neutral by using deionized water and ethanol, drying, grinding and sieving;
(2) 0.001mol of Bi (NO) is weighed 3 ) 3 ·5H 2 O、0.001mol Fe(NO 3 ) 3 .9H 2 Dissolving the weighed substances into 2M100mL dilute nitric acid under the action of magnetic stirring, and uniformly mixing;
(3) Under the action of magnetic stirring, adding 0.11g of glycine into the mixed solution obtained in the step (2), and uniformly mixing;
(4) Dropwise adding ammonia water until the pH value of the solution is 7 to obtain a precursor solution;
(5) Adding 3g of the halloysite nanotubes pretreated in the step (1) into the precursor solution obtained in the step (4), ultrasonically dispersing for 1.5h, heating in a water bath to 60 ℃, and magnetically stirring at the temperature for a period of time until the water is evaporated to dryness to obtain gel with certain fluidity;
(6) Placing the gel obtained in the step (5) in a muffle furnace, setting the furnace temperature to 250 ℃ to enable the gel to generate spontaneous combustion, finally cooling the gel to the room temperature by air, and grinding to obtain BiFeO 3 @ halloysite nanotube photo-fenton catalyst.
Example 2
This embodiment is basically the same as embodiment 1, except that: bi (NO) 3 ) 3 ·5H 2 The addition amount of O is 0.002mol 3 ) 3 The amount of 9H2O added was 0.002mol.
Example 3
This embodiment is basically the same as embodiment 1, except that: bi (NO) 3 ) 3 ·5H 2 The amount of O added was 0.003mol, fe (NO) 3 ) 3 The amount of 9H2O added was 0.003mol.
Example 4
This embodiment is basically the same as embodiment 1, except that: bi (NO) 3 ) 3 ·5H 2 The addition amount of O is 0.004mol 3 ) 3 The amount of 9H2O added was 0.004mol.
Example 5
This embodiment is basically the same as embodiment 1, except that: bi (NO) 3 ) 3 ·5H 2 O is added in an amount of 0.005mol and Fe (NO) 3 ) 3 The amount of 9H2O added was 0.005mol.
Example 6
The organic wastewater was degraded using the photo-fenton catalyst prepared in example 1~5, comprising the steps of:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
FIG. 1 shows the test chart of the methyl green degrading activity of the photo-Fenton catalyst obtained in example 1~5, and the photo-Fenton catalysts obtained in example 1~5 are respectively recorded as BiFeO 3 @ halloysite nanotube-1, biFeO 3 @ halloysite nanotube-2, biFeO 3 @ halloysite nanotube-3, biFeO 3 @ halloysite nanotube-4, biFeO 3 @ halloysite nanotube-5. As can be seen from FIG. 1, with Bi (NO) 3 ) 3 ·5H 2 O、Fe(NO 3 ) 3 .9H 2 The addition amount of O is increased, and the degradation rates of methyl green are 73.0%, 77.4%, 80.0%, 81.2% and 81.9% respectively after 60 min.
Example 7
The present example provides a method for preparing a photo-fenton catalyst, specifically comprising the following steps:
(1) Drying 10g of halloysite nanotubes, adding 5M 20mL sulfuric acid and 5M 100mL nitric acid, performing ultrasonic treatment for 5 hours at the temperature of 70 ℃, alternately cleaning the obtained product to be neutral by using deionized water and ethanol, drying, grinding and sieving;
(2) Weighing 1.46g Bi (NO) 3 ) 3 ·5H 2 O、1.21g Fe(NO 3 ) 3 .9H 2 Dissolving the weighed substances into 2M100mL dilute nitric acid under the action of magnetic stirring, and uniformly mixing;
(3) Under the action of magnetic stirring, adding 0.11g of glycine into the mixed solution obtained in the step (2), and uniformly mixing;
(4) Dropwise adding ammonia water until the pH value of the solution is 7 to obtain a precursor solution;
(5) Adding 3g of the halloysite nanotubes pretreated in the step (1) into the precursor solution obtained in the step (4), ultrasonically dispersing for 1.5h, heating in a water bath to 60 ℃, and magnetically stirring at the temperature for a period of time until the water is evaporated to dryness to obtain gel with certain fluidity;
(6) Condensing the gel obtained in the step (5)Placing the gel in a muffle furnace, setting the furnace temperature to 250 ℃ to ensure that the gel is subjected to spontaneous combustion, finally cooling the gel to room temperature by air, and grinding to obtain BiFeO 3 @ halloysite nanotube photo-fenton catalyst.
Example 8
This example is basically the same as example 7, except that: the amount of glycine added was 0.23g.
Example 9
This embodiment is basically the same as embodiment 7, except that: the amount of glycine added was 0.45g.
Example 10
The organic wastewater was degraded using the photo-fenton catalyst prepared in example 7~9, comprising the following steps:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
FIG. 2 shows the test chart of the methyl green degrading activity of the photo-Fenton catalyst obtained in example 7~9, and the photo-Fenton catalysts obtained in example 7~9 are respectively recorded as BiFeO 3 @ halloysite nanotube-1: 2. BiFeO 3 @ halloysite nanotube-1: 1. BiFeO 3 @ halloysite nanotube-2: 1. as can be seen from FIG. 2, with the increase of the glycine addition amount, the degradation rates of methyl green after 60min were 80.0%, 84.1% and 78.3%, respectively.
Example 11
The present example provides a method for preparing a photo-fenton catalyst, specifically comprising the following steps:
(1) Drying 10g of halloysite nanotubes, adding 5M 20mL sulfuric acid and 5M 100mL nitric acid, performing ultrasonic treatment at the temperature of 70 ℃ for 5 hours, alternately cleaning the obtained product to be neutral by using deionized water and ethanol, drying, grinding and sieving;
(2) 1.46g of Bi (NO) are weighed out 3 ) 3 ·5H 2 O、1.21g Fe(NO 3 ) 3 9H2O, dissolving the weighed substances in 2M100mL dilute nitric acid under the action of magnetic stirring, and uniformly mixing;
(3) Adding 0.23g of glycine into the mixed solution obtained in the step (2) under the action of magnetic stirring, and uniformly mixing;
(4) Dropwise adding ammonia water until the pH value of the solution is 4 to obtain a precursor solution;
(5) Adding 3g of the halloysite nanotubes pretreated in the step (1) into the precursor solution obtained in the step (4), ultrasonically dispersing for 1.5h, heating in a water bath to 60 ℃, and magnetically stirring at the temperature for a period of time until the water is evaporated to dryness to obtain gel with certain fluidity;
(6) Placing the gel obtained in the step (5) in a muffle furnace, setting the furnace temperature to 250 ℃ to enable the gel to generate spontaneous combustion, finally cooling the gel to the room temperature by air, and grinding to obtain BiFeO 3 @ halloysite nanotube photo-fenton catalyst.
Example 12
This embodiment is basically the same as embodiment 11, except that: in the step (4), ammonia water is added until the pH value of the solution is 6.
Example 13
This embodiment is basically the same as embodiment 11, except that: in the step (4), ammonia water is added until the pH value of the solution is 7.
Example 14
This embodiment is basically the same as embodiment 11, except that: in the step (4), ammonia water is added until the pH value of the solution is 8.
Example 15
This embodiment is basically the same as embodiment 11, except that: in the step (4), ammonia water is added until the pH value of the solution is 10.
Example 16
The organic wastewater was degraded by using the photo-Fenton catalysts prepared in examples 11 to 15, and the specific steps were as follows:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
The activity test charts of the photo-Fenton catalysts obtained in examples 11 to 15 for degrading methyl green are shown in FIG. 3, and the photo-Fenton catalysts obtained in examples 11 to 15 are respectively recorded as BiFeO 3 @ halloysite nanotubes-pH 4, biFeO 3 @ halloysite nanotube-pH 6, biFeO 3 @ halloysite nanotube-pH 7, biFeO 3 @ halloysite nanotubes-pH 8, biFeO 3 @ halloysite nanotubes-pH 10. As can be seen from fig. 3, the degradation rates of methyl green after 60min were 65.4%, 79.2%, 84.1%, 85.3%, 87.1% respectively with increasing pH.
Example 17
The present example provides a method for preparing a photo-fenton catalyst, which specifically comprises the following steps:
(1) Drying 10g of halloysite nanotubes, adding 5M 20mL sulfuric acid and 5M 100mL nitric acid, performing ultrasonic treatment for 5 hours at the temperature of 70 ℃, alternately cleaning the obtained product to be neutral by using deionized water and ethanol, drying, grinding and sieving;
(2) 1.46g of Bi (NO) are weighed out 3 ) 3 .5H 2 O、1.21g Fe(NO 3 ) 3 .9H 2 Dissolving the weighed substances into 2M100mL of dilute nitric acid under the action of magnetic stirring, and uniformly mixing;
(3) Under the action of magnetic stirring, adding 0.23g of glycine into the mixed solution obtained in the step (2), and uniformly mixing;
(4) Dropwise adding ammonia water until the pH value of the solution is 7 to obtain a precursor solution;
(5) Adding 3g of the halloysite nanotubes pretreated in the step (1) into the precursor solution obtained in the step (4), ultrasonically dispersing for 1.5h, heating in a water bath to 60 ℃, and magnetically stirring at the temperature for a period of time until the water is evaporated to dryness to obtain gel with certain fluidity;
(6) Placing the gel obtained in the step (5) in a muffle furnace, setting the furnace temperature to 250 ℃ to enable the gel to generate spontaneous combustion, finally cooling the gel to the room temperature by air, and grinding to obtain BiFeO 3 @ halloysite nanotube photo-fenton catalyst.
Example 18
This embodiment is basically the same as embodiment 17, except that: in the step (5), the temperature of the water bath is 75 ℃.
Example 19
This example is basically the same as example 17, except that: in the step (5), the temperature of the water bath is 90 ℃.
Example 20
The organic wastewater was degraded by using the photo-Fenton catalysts prepared in examples 17 to 19, and the specific steps were as follows:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
The test charts of the activity of the photo-Fenton catalysts obtained in examples 17 to 19 for degrading methyl Green are shown in FIG. 4, and the photo-Fenton catalysts obtained in examples 17 to 19 are respectively recorded as BiFeO 3 @ halloysite nanotube-60 ℃ BiFeO 3 @ halloysite nanotube-75 ℃ BiFeO 3 @ halloysite nanotubes-90 ℃. As can be seen from FIG. 4, the degradation rates of methyl green after 60min were 84.1%, 87.2% and 88.0% respectively with increasing temperature of the water bath.
Example 21
The present example provides a method for preparing a photo-fenton catalyst, which specifically comprises the following steps:
(1) Drying 10g of halloysite nanotubes, adding 5M 20mL sulfuric acid and 5M 100mL nitric acid, performing ultrasonic treatment at the temperature of 70 ℃ for 5 hours, alternately cleaning the obtained product to be neutral by using deionized water and ethanol, drying, grinding and sieving;
(2) 1.46g of Bi (NO) are weighed out 3 ) 3 .5H2O、1.21g Fe(NO 3 ) 3 9H2O, dissolving the weighed substances into 2M100mL of dilute nitric acid under the action of magnetic stirring, and uniformly mixing;
(3) Under the action of magnetic stirring, adding 0.23g of glycine into the mixed solution obtained in the step (2), and uniformly mixing;
(4) Dropwise adding ammonia water until the pH value of the solution is 7 to obtain a precursor solution;
(5) Adding 3g of the halloysite nanotube pretreated in the step (1) into the precursor solution obtained in the step (4), ultrasonically dispersing for 1.5h, heating in a water bath to 75 ℃, and magnetically stirring at the temperature for a period of time until the water is evaporated to dryness to obtain gel with certain fluidity;
(6) Placing the gel obtained in the step (5) in a muffle furnace, setting the furnace temperature to 250 ℃ to enable the gel to generate spontaneous combustion, finally cooling the gel to the room temperature by air, and grinding to obtain BiFeO 3 @ halloysite nanotube photo-fenton catalyst.
Example 22
This example is basically the same as example 21, except that: in the step (6), the furnace temperature is set to 350 ℃.
Example 23
This embodiment is basically the same as embodiment 18, except that: in the step (6), the furnace temperature is set to 450 ℃.
Example 24
The organic wastewater was degraded by using the photo-Fenton catalysts prepared in examples 21 to 23, and the specific steps were as follows:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
photo-Fenton obtained in examples 21 to 23FIG. 5 shows the test chart of the activity of the catalyst for degrading methyl green, and the photo-Fenton catalysts obtained in examples 21 to 23 were recorded as BiFeO 3 @ halloysite nanotube-250 ℃ BiFeO 3 @ halloysite nanotube-350 ℃ BiFeO 3 @ halloysite nanotubes-450 ℃. As can be seen from fig. 5, the degradation rates of methyl green after 60min were 87.2%, 90.8% and 92.9% respectively with increasing furnace temperature.
Example 25
BiFeO synthesized in example 22 was used 3 The method for degrading the organic wastewater by using the @ halloysite nanotube photo-Fenton catalyst comprises the following specific steps of:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.1g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
Example 26
This embodiment is basically the same as embodiment 25, except that: 0.2g of photo-Fenton's catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate were added to 1L of the organic wastewater.
Example 27
This embodiment is basically the same as embodiment 25, except that: 0.4g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate were added to 1L of the organic wastewater.
The test patterns of the activity of degrading methyl green in examples 25 to 27 are shown in FIG. 6, and it can be seen that: with the increase of the catalyst adding amount, the degradation rates of methyl green are respectively 86.0%, 92.9% and 94.0%.
Example 28
BiFeO synthesized in example 22 was used 3 The method for degrading the organic wastewater by using the @ halloysite nanotube photo-Fenton catalyst comprises the following specific steps of:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 5mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
Examples 29 to 31
Examples 29 to 31 are basically the same as example 28, except that: the addition amount of hydrogen peroxide in each 1L of organic wastewater is 10mM, 15mM and 20mM respectively.
The test patterns of the activity of degrading methyl green in examples 28 to 31 are shown in FIG. 7, and it can be seen that: with the increase of the hydrogen peroxide concentration, the degradation rates of methyl green are 67.8%, 92.9%, 93.5% and 94.1%, respectively.
Example 32
BiFeO synthesized in example 22 was used 3 The method for degrading the organic wastewater by using the @ halloysite nanotube photo-Fenton catalyst comprises the following specific steps of:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
Examples 33 to 37
Examples 33 to 37 are substantially the same as example 32 except that: the adding amount of the sodium oxalate in each 1L of the organic wastewater is respectively 0.02, 0.04, 0.06, 0.08 and 0.1g.
The test patterns of the activity of degrading methyl green in examples 32 to 37 are shown in FIG. 8, and it can be seen that: with the increase of the hydrogen peroxide concentration, the degradation rates of methyl green are 93.9%, 95.0%, 96.3%, 98.8%, 95.9% and 94.0%, respectively.
Example 38
BiFeO synthesized in example 22 was used 3 The method for degrading organic wastewater by using the @ halloysite nanotube photo-Fenton catalyst comprises the following specific steps of:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0.06g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
Examples 39 to 42
Examples 39 to 42 are substantially the same as example 38, except that: the pH was adjusted to 5, 7, 9, 11 with 3M sulfuric acid solution and 3M sodium hydroxide solution, respectively.
The test patterns of the activity of degrading methyl green in examples 38 to 42 are shown in FIG. 9, and it can be seen that: with the increase of the hydrogen peroxide concentration, the degradation rates of methyl green are respectively 98.8%, 97.3%, 95.4%, 91.4% and 88.0%.
Example 43
BiFeO synthesized in example 22 was used 3 The method for degrading the organic wastewater by using the @ halloysite nanotube photo-Fenton catalyst comprises the following specific steps of:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Subsequently, the photo-fenton catalyst was recovered by a magnet, dried, continuously mixed with hydrogen peroxide, catalytically degraded under uv illumination, and the process was repeated 4 times.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0.06g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
The test chart of the activity of degrading methyl green in this example is shown in fig. 10, and it can be seen that the photo-fenton catalyst still shows higher catalytic activity after 5 cycles, which indicates that the prepared photo-fenton catalyst has good stability and recoverability.
Comparative example 1
Drying 10g of halloysite nanotubes, adding 5M sulfuric acid and 5M nitric acid, carrying out ultrasonic treatment at 70 ℃ for 5h, alternately cleaning the obtained product to be neutral by using deionized water and ethanol, drying, grinding and sieving;
the method for degrading organic wastewater by using the photo-Fenton catalyst synthesized in the comparative example comprises the following specific steps:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0.06g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
After 60min, the methyl green degradation rate is 39.23%.
Comparative example 2
(1) 1.46g of Bi (NO) are weighed out 3 ) 3 .5H2O、1.21g Fe(NO 3 ) 3 9H2O, dissolving the weighed substances into 2M100mL of dilute nitric acid under the action of magnetic stirring, and uniformly mixing;
(2) Under the action of magnetic stirring, adding 0.23g of glycine into the mixed solution obtained in the step (1), and uniformly mixing;
(3) Dropwise adding ammonia water until the pH value of the solution is 7 to obtain a precursor solution;
(4) Heating the precursor solution obtained in the step (3) to 80 ℃ in a water bath, and magnetically stirring at the temperature for a period of time until the water is evaporated to dryness to obtain gel with certain fluidity;
(5) Placing the gel obtained in the step (4) in a muffle furnace, setting the furnace temperature to 250 ℃ to enable the gel to generate spontaneous combustion, finally cooling the gel to the room temperature by air, and grinding to obtain BiFeO 3 A material.
The method for degrading organic wastewater by using the photo-Fenton catalyst synthesized in the comparative example comprises the following specific steps:
the method comprises the steps of taking 500mL of 100mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0.06g of sodium oxalate are added into each 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
After 60min, the methyl green degradation rate is 72.43%.
Comparative example 3
BiFeO synthesized in example 22 was used 3 The method for degrading the organic wastewater by using the @ halloysite nanotube photo-Fenton catalyst comprises the following specific steps of:
the method comprises the steps of taking 500mL of 200mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
After 60min, the methyl green degradation rate is 90.9%.
Comparative example 4
BiFeO synthesized in example 22 was used 3 The method for degrading the organic wastewater by using the @ halloysite nanotube photo-Fenton catalyst comprises the following specific steps of:
500mL of 200mg/L organic pollutants are used as degradation objects, the pH value is adjusted to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate are added, and a UV Fenton experiment is carried out on the organic pollutants for 60min under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0.06g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
After 60min, the methyl green degradation rate is 96.6%.
Comparative example 5
Using reference "Maleki A ， Hajizadeh Z ， Salehi P.Mesoporoushalloysite nanotubes modified by CuFe2O4 spinel ferrite nanoparticles and studyof its application as a novel and efficient heterogethylene catalyst in the synthesis of pyrazolopyridine derivatives Sci Rep.2019 Apr 3 (1): 5552 the process of "CuFe 2 O 4 @ HNTs composite material.
Using reference "Zhang ， Ao-Bo et al. “Facile preparation of MnFe 2 O 4 "RSC Advances 4 (2014)" has been described: 13565-13568, the method for preparing MnFe 2 O 4 /HNTs nanocomposites.
Using reference "Ghiyasiyan-Arani M ， Salavati-Niasari M.Decoration of green synthesized S ， N-GQDs and CoFe2O4 on halophysical as natural substrate for electrochemical hydrogen storage application. Sci Rep. 2022 May 16 (1): 8103.", coFe2O4/HNTs nanocomposite material.
Using reference "Chen Zihao ， Mu Dawei ， Yang Huaming ， Ouyang Jing preparation and Performance control of barium ferrite/halloysite composites [ J]Functional material ， 2021 ， 52 (01): 1011-1016, preparing the barium ferrite/halloysite composite material.
Reference Ling Jiang preparation of magnesium ferrite composite and removal mechanism study of heavy metal ions [ D]Combined fertilizer industry university ， 2019, the method in the specification is used for preparing the magnesium ferrite/halloysite composite material.
Using the reference patent "Liu Lihua ， Su Gang ， Niu Mengyuan ， Kuang Qiujuan ， Tang Anping ， Liu Xing ， Xue Jianrong bismuth ferrite/sepiolite composite visible light catalyst and preparation method thereof [ P]The province of Hunan province: CN112774686A ， 2021-05-11 "to prepare the bismuth ferrite/sepiolite composite material.
Using reference "Li Tie ， Li Yue ， Wang Yingyi ， Zhang preparation of graphene-bismuth ferrite nanocrystalline composite material and catalytic performance research thereof [ J]Journal of inorganic materials ， 2021 ， 36 (07): 725-732.
BiFeO synthesized in example 22 was used 3 @ halloysite nanotube photo-Fenton catalyst and CuFe 2 O 4 @ HNTs composite material, mnFe 2 O 4 /HNTs nanocomposite, coFe 2 O 4 The method comprises the following steps of degrading organic wastewater by using a/HNTs nano composite material, a barium ferrite/halloysite composite material, a magnesium ferrite/halloysite composite material, a bismuth ferrite/sepiolite composite material and a graphene-bismuth ferrite composite material, and specifically comprises the following steps:
the method comprises the steps of taking 500mL of 200mg/L organic pollutants as degradation objects, adjusting the pH value to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, adding a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate, and carrying out a 60-min UV Fenton experiment under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0.06g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
After 60min, biFeO synthesized in example 22 3 @ halloysite nanotube photo-Fenton catalyst and CuFe 2 O 4 @ HNTs composite material, mnFe 2 O 4 /HNTs nanocomposite and CoFe 2 O 4 The methyl green degradation rates of the/HNTs nano composite material, the barium ferrite/halloysite composite material, the magnesium ferrite/halloysite composite material, the bismuth ferrite/sepiolite composite material and the graphene-bismuth ferrite composite material are 98.8%, 95.4%, 93.0%, 91.0%, 92.7%, 89.3%, 86.4% and 89.3% in sequence.
Comparative example 6
This comparative example used BiFeO synthesized in example 22 3 The method for degrading the organic wastewater by using the @ halloysite nanotube photo-Fenton catalyst comprises the following specific steps of:
500mL of 200mg/L organic pollutants are used as degradation objects, the pH value is adjusted to 3 by using a 3M sulfuric acid solution and a 3M sodium hydroxide solution, a photo-Fenton catalyst, hydrogen peroxide and sodium oxalate are added, and a UV Fenton experiment is carried out on the organic pollutants for 60min under the irradiation of ultraviolet light.
Wherein, 0.2g of photo-Fenton catalyst, 10mM of hydrogen peroxide and 0g of sodium oxalate are added into every 1L of organic wastewater; the organic pollutant in the organic wastewater is methyl green.
After 60min, the methyl green degradation rate was 90.9%.
Comparative examples 7 to 10
Comparative examples 7 to 10 are substantially the same as comparative example 6, except that: the pH was adjusted to 5, 7, 9, 11 using 3M sulfuric acid solution and 3M sodium hydroxide solution.
The degradation rates of methyl greens in comparative examples 6 to 10 were 93.9%, 91.2%, 88.0%, 85.0%, and 81.4%, respectively, as the pH increased. Therefore, the photo-Fenton catalyst has a wide pH application range.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A preparation method of a photo-Fenton catalyst for degrading methyl green is characterized by comprising the following steps:
(1) Adding a halloysite nanotube into a mixed acid solution of sulfuric acid and nitric acid, performing ultrasonic treatment at the temperature of 60-80 ℃ for 4-6 h, cleaning, drying and grinding the obtained product to obtain a pretreated halloysite nanotube;
(2) Dissolving bismuth nitrate and ferric nitrate in dilute nitric acid, uniformly mixing, adding glycine, and then dropwise adding ammonia water until the pH value of the solution is 7 to 10 to obtain a precursor solution;
(3) Mixing the precursor solution obtained in the step (2) with the pretreated halloysite nanotube obtained in the step (1) for ultrasonic dispersion, and heating until the water in the solution is evaporated to dryness to form gel;
(4) Placing the gel obtained in the step (3) in a furnace, setting the furnace temperature to enable the gel to be subjected to spontaneous combustion, then cooling to room temperature, and grinding to obtain BiFeO 3 @ halloysite nanotube photo-fenton catalyst;
wherein: in the step (1), the concentration of the sulfuric acid is 3 to 5mol/L, and the concentration of the nitric acid is 3 to 5mol/L; the volume ratio of the sulfuric acid to the nitric acid is 1:3~1:5; the liquid-solid ratio of the nitric acid to the halloysite nanotube is 10 to 15mL/g;
in the step (2), the concentration of the dilute nitric acid is 2 to 3mol/L; the bismuth nitrate: iron nitrate: the dosage ratio of the dilute nitric acid is 0.001 to 0.005mol:0.001 to 0.005mol:100mL, wherein the ratio of bismuth nitrate: the molar ratio of ferric nitrate is 1:1; the molar ratio of glycine to bismuth nitrate is 1:1~2:1;
in the step (3), the solid-to-liquid ratio of the pretreated halloysite nanotube to the precursor solution is 2-3g/100 mL, and the heating temperature is 60-90 ℃.
2. The method according to claim 1, wherein the washing in the step (1) is specifically: and alternately cleaning the mixture to be neutral by using deionized water and ethanol.
3. The preparation method according to claim 1, wherein in the step (4), the oven temperature is set to be 250 to 450 ℃, and the gel is spontaneously combusted.
4. The use of a photo-Fenton catalyst prepared by the method of any one of claims 1~3 in the treatment of organic wastewater, comprising the steps of:
s1, placing organic wastewater into a reaction container, and adjusting the pH to 3 to 11, wherein organic matters in the organic wastewater comprise methyl green;
step S2, adding hydrogen peroxide, a photo-Fenton catalyst and oxalic acid or sodium oxalate into a reaction container; adding 0.1-0.4 g of photo-Fenton catalyst, 5-20mmol of hydrogen peroxide and 0-0.1g of sodium oxalate or oxalic acid into every 1L of organic wastewater;
and S3, carrying out UV Fenton degradation reaction under the irradiation of ultraviolet light.
5. The application of claim 4, wherein in the step S1, the organic matters in the organic wastewater comprise methyl green, and the mass concentration of the methyl green is 100 to 200mg/L; the pH was adjusted to 3 to 11 with 2 to 3mol/L sulfuric acid solution and 2 to 3mol/L sodium hydroxide solution.
6. The use according to claim 4, wherein in step S2, 0.1 to 0.4g of photo-Fenton catalyst, 5 to 20mmol of hydrogen peroxide, 0 to 0.1g of sodium oxalate or oxalic acid are added into every 1L of organic wastewater; in the step S3, a low-pressure mercury lamp is adopted, the illumination time is 1 to 4 hours, and the reaction temperature is 20 to 25 ℃.
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