CN108686656B - alpha-Fe2O3Coal gangue composite photocatalyst and preparation method and application thereof - Google Patents
alpha-Fe2O3Coal gangue composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003245 coal Substances 0.000 claims abstract description 100
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 13
- 150000002505 iron Chemical class 0.000 claims abstract description 11
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical class OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
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- 238000001354 calcination Methods 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
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- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 28
- 230000001699 photocatalysis Effects 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002245 particle Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 230000009466 transformation Effects 0.000 description 2
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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Abstract
The invention relates to alpha-Fe2O3The coal gangue composite photocatalyst is prepared from the following raw materials by boiling reflux: the pretreated coal gangue and the aqueous solution of ferric salt; the aqueous solution of the iron salt is alpha-Fe2O3The mass ratio of the mass meter to the pretreated coal gangue is 0.5-5: 100. The invention also relates to a method for preparing the composite photocatalyst and application thereof. The product of the invention can effectively degrade chlorophenol compounds under the condition of ultraviolet illumination. The preparation method has the characteristics of less raw materials, simple process, short reaction time, relatively mild conditions and no pollution to the environment, is a green synthesis process, and is easy to realize industrialization.
Description
Technical Field
The invention belongs to the field of photocatalyst preparation, and particularly relates to alpha-Fe2O3Coal gangue composite photocatalyst, preparation method thereof and application thereof in degrading chlorophenol compounds.
Background
The photocatalysis technology can directly utilize light energy to degrade organic pollutants into inorganic micromolecules at normal temperature and normal pressure, has the characteristics of low energy consumption, simple and convenient operation, mild reaction conditions and small secondary pollution, and is an ideal environmental pollution treatment technology. At present, the shortage of fossil energy and the serious environmental pollution are increasing, the importance of the photocatalytic technology is self-evident, and the core of the technology is to research and develop the photocatalyst with excellent performance.
Common photocatalytic materials are primarily TiO2、SnO2、CdS、WO3、ZrO2And Fe2O3And the like. alpha-Fe2O3The solar cell has the advantages of narrow forbidden band width, light absorption range expanded to a visible light region, good utilization of sunlight, high chemical stability, acid and alkali resistance, light and corrosion resistance, no toxicity, low price and other excellent characteristics, and only the photocatalytic efficiency needs to be improved.
Because the activity of the photocatalyst is closely related to the size of the particle size of the photocatalyst, the smaller the particle size, the larger the specific surface area and the higher the photocatalytic activity, most semiconductor photocatalysts are micron/nano particles. However, in the process of photocatalytic degradation of organic pollutants, the micro/nano particles can also cause secondary agglomeration due to too small particle size, and have the defects of difficult recovery after use and easy formation of secondary pollution. This has become a technical bottleneck restricting the popularization and application of micro/nano semiconductor photocatalysts.
As an effective means for solving the above problems, the immobilization of micro/nano semiconductor photocatalysts has recently received increasing attention from researchers at home and abroad. At present, commonly used immobilization methods are generally divided into two types, namely film formation immobilization and carrier immobilization, and in the latter method, activated carbon, carbon nanotubes and the like with developed pore structures and large specific surface areas are mostly selected as carriers. Because they are expensive, their industrialization is slow.
The coal gangue is a gray black rock with carbon content lower than that of coal, which is associated and symbiotic with a coal bed in the coal forming process. The solid waste discharged in the coal mining, washing and processing processes accounts for 15-20% of the coal yield. A large amount of unused coal gangue is randomly accumulated, which occupies land and pollutes environment. The deep development of the comprehensive utilization of the coal gangue is a fundamental way for the deep transformation and sustainable development of the coal industry in China. The natural coal gangue has complex components and compact structure, but after modification, inorganic minerals in the coal gangue are converted from a crystalline state part to an amorphous state, the structure of the inorganic minerals is loosened, the specific surface area is increased, the pore structure is developed, and the adsorption performance is obviously improved.
To date, no alpha-Fe has been found2O3A report of a coal gangue composite photocatalyst. If the modified coal gangue is used as an adsorption carrier to load micro/nano alpha-Fe2O3Particles of alpha-Fe2O3The coal gangue composite photocatalyst not only changes the coal gangue into valuable, realizes the effective utilization of resources, but also is beneficial to improving the micro/nano alpha-Fe2O3The photocatalytic efficiency of (c). Therefore, the method for preparing the green and environment-friendly alpha-Fe with simple process, low cost, low energy consumption2O3The preparation method of the coal gangue composite photocatalyst has important practical significance.
Disclosure of Invention
The invention aims to provide alpha-Fe2O3A coal gangue composite photocatalyst and a preparation method thereof. The preparation method has the characteristics of few raw materials, simple process, short reaction time, relatively mild conditions and no pollution to the environment, is a green synthesis process, and is easy to realize industrialization. The prepared product can effectively degrade chlorophenol compounds under the condition of ultraviolet illumination.
The invention adopts the following technical scheme:
alpha-Fe2O3The coal gangue composite photocatalyst is prepared from the following raw materials by boiling reflux: the pretreated coal gangue and the aqueous solution of ferric salt; the aqueous solution of the iron salt is alpha-Fe2O3The mass ratio of the mass meter to the pretreated coal gangue is 0.5-5: 100.
The parameters of the aqueous solution of the iron salt are calculated by the following formula:
m α-Fe2O3= C aqueous solutions of iron salts×V Aqueous solutions of iron salts×M α-Fe2O3
In the formula (I), the compound is shown in the specification,C-molar concentration, mol/L;V-volume, L;M-molar mass, g/mol;m-mass, g.
Furthermore, the pretreated coal gangue is prepared by crushing and grinding coal gangue, sieving the crushed coal gangue with a 150-300-mesh sieve, and calcining the coal gangue at 700-900 ℃ for 1.5-3 h for later use.
Preferably, the pretreated coal gangue is prepared by crushing and grinding coal gangue, sieving with a 200-mesh sieve, and calcining at 800 ℃ for 2 h for later use.
Further, the iron salt includes ferric nitrate, ferric chloride or ferric sulfate.
Further, Fe in the aqueous solution of the iron salt3+The concentration of the ions was 0.4 mol/L.
The alpha-Fe2O3The preparation method of the coal gangue composite photocatalyst comprises the following steps:
(1) taking coal gangue, crushing, grinding, sieving with a 150-300 mesh sieve, and calcining at 700-900 ℃ for 1.5-3 h to obtain pretreated coal gangue;
(2) preparation of Fe3+An iron salt aqueous solution with an ion concentration of 0.4 mol/L;
(3) taking 5 mL of the aqueous solution of the ferric salt prepared in the step (2), adding distilled water to a constant volume of 100 mL, adding the pretreated coal gangue obtained in the step (1) into the solution, and magnetically stirring for 1 h;
the aqueous solution of the iron salt is alpha-Fe2O3Mass meter, alpha-Fe2O3The mass ratio of the coal gangue to the pretreated coal gangue is 0.5-5: 100;
(4) adjusting the pH value of the reaction system obtained in the step (3) to 9-11, and then boiling and refluxing for 3 h;
(5) after the processes of suction filtration, washing by distilled water and natural drying, alpha-Fe is obtained2O3A coal gangue composite photocatalyst.
In the step (1), the coal gangue is crushed and ground and then is sieved by a 200-mesh sieve, the calcining temperature is 800 ℃, and the calcining time is 2 hours.
Wherein in the step (2), the ferric salt is ferric nitrate, ferric chloride or ferric sulfate.
Wherein, in the step (3), the alpha-Fe2O3The mass ratio of the coal gangue to the pretreated coal gangue is 1-4: 100, and preferably 3: 100.
Wherein in the step (4), the pH value of the reaction system is 10.
In the step (4), 6 mol/L and 0.1 mol/L aqueous solution of sodium hydroxide are used for adjusting the pH value of the reaction system.
The alpha-Fe2O3Application of the coal gangue composite photocatalyst in degradation of chlorophenol compounds.
The invention has the beneficial effects that: the natural coal gangue has larger granularity, hard texture and compact structure, and is difficult to be directly applied. It is usually first crushed, ground, sieved and calcined. The natural coal gangue is crushed and ground to ensure that the particle size of the natural coal gangue is rapidly reduced, the crystal lattice is distorted, and the specific surface area is correspondingly increased, but the structure of the coal gangue particles is still compact, the adsorbability is still poor, and the activity is not basically shown when the chemical reaction is carried out. After high-temperature calcination treatment, certain components of the coal gangue are volatilized, and some inorganic compounds can also generate crystalline state transformation, so that the structural porosity and the chemical activity of the coal gangue are greatly improved. Although the above treatments all play a role in improving the performance of the coal gangue, the effect is far from sufficient for the coal gangue to be used as an adsorbent. The calcined coal gangue is further treated by acid or alkali.
The acid solution can dissolve the oxides of Al, Fe and Ca in the coal gangue, and increase the porosity of coal gangue particles, thereby enhancing the adsorption capacity of the coal gangue. The alkaline solution can dissolve some metal oxides in the coal gangue, increase the porosity of coal gangue particles, and a proper amount of alkali can react with oxides of Si and Al in the coal gangue to generate the zeolite molecular sieve with better adsorption capacity.
It is well known that the ability of a photocatalyst to adsorb degraded materials is an important factor affecting its photocatalytic efficiency. Improvement ofThe gangue has large specific surface area, multiple micropores and good adsorbability, and is favorable for loading alpha-Fe by a chemical method2O3Photocatalyst, alpha-Fe formed2O3The gangue composite photocatalyst can also realize alpha-Fe2O3The synergistic effect of the coal gangue and the catalyst can keep higher pollutant concentration on the surface of the catalyst all the time and promote alpha-Fe2O3The electron transfer between the degraded substance and the degraded substance molecule improves the alpha-Fe2O3The photocatalytic efficiency of (c).
Earlier researches show that micro/nano alpha-Fe with good photocatalytic performance can be obtained by taking ferric salt and alkali as reactants and adopting a boiling reflux method under the condition of pH 9-112O3The finding that this allows the preparation of alpha-Fe in one step2O3The coal gangue composite becomes possible. The alkali existing in the reaction system can modify coal gangue and can be adsorbed with Fe absorbed by the modified coal gangue3+Ion reaction to obtain alpha-Fe2O3Thereby converting alpha-Fe2O3Is loaded on the modified coal gangue. The method has the advantages of less raw materials, simple process, short reaction time, relatively mild conditions and no pollution to the environment, and is a green synthesis process.
Drawings
FIG. 1 shows modified coal gangue and pure alpha-Fe2O3And alpha-Fe2O3XRD spectrum of the/coal gangue composite.
In FIG. 1, a is modified coal gangue and b is pure alpha-Fe2O3C is alpha-Fe2O3A coal gangue composite.
FIG. 2 is pure α -Fe2O3And different mass ratios of alpha-Fe2O3The curve of the efficiency of the coal gangue composite photocatalytic degradation of pentachlorophenol changes with time.
Detailed Description
For the purpose of enhancing an understanding of the present invention, the present invention will be described in detail with reference to the accompanying drawings and examples, which are illustrative only and are not intended to limit the scope of the present invention.
Example 1
Coal gangue from Shanxi Parathaea is crushed and fully ground, and then is sieved by a 200-mesh sieve and calcined for 2 hours at 700 ℃ for later use. At the same time, Fe is prepared3+The iron salt aqueous solution with the ion concentration of 0.4 mol/L, the sodium hydroxide aqueous solution with the ion concentration of 6 mol/L and 0.1 mol/L are reserved.
5 mL of an aqueous ferric nitrate solution (Fe)3+Ion concentration of 0.4 mol/L) is introduced into a three-neck flask, distilled water is used for fixing the volume to 100 mL, the calculated amount of pretreated gangue powder is added, after magnetic stirring is carried out for 1 h, 6 mol/L and 0.1 mol/L sodium hydroxide aqueous solution is slowly dripped into the flask, the pH value of a reaction system is adjusted to 9 by controlling the addition amount of the sodium hydroxide aqueous solution, and boiling reflux is carried out for 3 h. Filtering, washing with distilled water, and naturally drying to obtain alpha-Fe2O3A coal gangue composite photocatalyst.
Examples 2 to 6 and comparative examples 1 to 2
The operation steps of examples 2 to 6 and comparative examples 1 to 2 are the same as those of example 1, and the differences are only the type of iron salt used, the calcining temperature of the coal gangue, the amount of the coal gangue and the pH value of the reaction system, which are specifically shown in Table 1.
TABLE 1 EXAMPLES 2-6 AND COMPARATIVE EXAMPLES 1-2
Effect example 1 XRD characterization
FIG. 1 shows modified coal gangue and pure alpha-Fe2O3And alpha-Fe2O3XRD spectrum of the/coal gangue composite. In FIG. 1c, 2 simultaneously appearsθDiffraction peaks (fig. 1 a) and 2 of modified coal gangue at 21.18 ° and 26.64 °θα -Fe of hexagonal structure at =24.08 °, 33.19 °, 35.67 °, 40.84 °, 49.47 °, 53.97 °, 57.46 °, 62.39 °, 63.96 °2O3(JCPDS 33-0664) (FIG. 1 b), confirming that the product is alpha-Fe2O3A coal gangue composite. Because of alpha-Fe2O3Covering the surface of the modified coal gangue, so that the alpha-Fe2O3Coal gangue compositionIn which is alpha-Fe2O3Each diffraction peak intensity of (1) is relatively pure alpha-Fe2O3The change is not great, but the diffraction peak intensity of the modified coal gangue is less than that of the non-loaded alpha-Fe2O3The previous is significantly reduced.
Effect example 2 alpha-Fe2O3Photocatalytic performance evaluation of coal gangue composite
Chlorophenols are a typical "carcinogenic, teratogenic, mutagenic" class of organic pollutants, and are widely used in the production of preservatives, dyes, herbicides, insecticides, and the like. Meanwhile, chlorophenols byproducts are also possibly generated in the processes of waste incineration, pulp bleaching and drinking water chlorination disinfection. Common chlorophenols are 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, 2,3,4, 6-tetrachlorophenol, pentachlorophenol, etc. The heavy use of this organic compound, the early lack of awareness of its toxicity and hazards, and the concomitant long-term neglect, has led to its constant accumulation in the environment, with direct damage and potential threat to the aquatic environment and human health. However, it is difficult for the conventional water treatment method and biotechnology to effectively degrade chlorophenols. In recent years, advanced oxidation technologies represented by photocatalysis are rapidly developed in the aspect of pollutant environmental management, and the research of applying the advanced oxidation technologies to degradation of chlorophenol compounds also achieves remarkable results.
The result of the photocatalytic performance evaluation experiment shows that the prepared alpha-Fe2O3The coal gangue composite has better degradation effect on the chlorophenol compounds. The experimental steps and data for evaluating the photocatalytic performance by taking pentachlorophenol as a target degradation product are as follows:
adding 100 mL of pentachlorophenol solution (10 mg/L, pH 9-10) and 0.1 g of alpha-Fe into a beaker2O3The coal gangue composite powder is stirred for 30 min in a dark and strong way, so that the pentachlorophenol achieves the adsorption-desorption balance on the surface of the catalyst. Then, under magnetic stirring, the mixture was irradiated with a 125W high-pressure mercury lamp (lamp-liquid surface distance: 10 cm) and the timer was started. Sampling at intervals, centrifuging, filtering the supernatant with microporous membrane, and measuring the maximum absorption wavelength of pentachlorophenol with ultraviolet-visible spectrophotometerλ max= 220 nm) of the substrateAbsorbance and the degradation rate of pentachlorophenol was calculated according to the following formula (η）：
η=(A 0−A t)/A 0×100%
In the formula (I), the compound is shown in the specification,A 0the absorbance of the pentachlorophenol solution before illumination;A tthe absorbance of the pentachlorophenol solution after the illumination time t is shown.
FIG. 2 is pure α -Fe2O3And different mass ratios of alpha-Fe2O3The curve of the efficiency of the coal gangue composite photocatalytic degradation of pentachlorophenol changes with time. The blank experiment shows that the degradation rate of the pentachlorophenol after 180 min is only 46.92% when irradiated by ultraviolet light, which is the self-decomposition of the pentachlorophenol. Pure alpha-Fe is added while ultraviolet irradiation is carried out2O3Or alpha-Fe2O3The coal gangue composite photocatalyst has the advantage that the degradation rate of pentachlorophenol is remarkably improved within the same illumination time. It was observed that all of the alpha-Fe2O3The photocatalytic activity of the coal gangue composite is higher than that of pure alpha-Fe2O3This confirmed that alpha-Fe2O3alpha-Fe in coal gangue composite2O3And a synergistic effect is indeed existed between the coal gangue. However, alpha-Fe2O3The mass ratio of the alpha-Fe to the coal gangue is not larger, but is better, and the mass ratio is 3:1002O3The coal gangue compound shows the highest photocatalytic activity, and the degradation rate of the pentachlorophenol is close to 90% within 180 min.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, but not restrictive, and those skilled in the art can easily understand the spirit of the present invention from the above-mentioned embodiments and make various extensions and changes, but they are within the scope of the present invention without departing from the spirit of the present invention.
Claims (7)
1. alpha-Fe2O3The preparation method of the coal gangue composite photocatalyst is characterized by comprising the following steps:
(1) taking coal gangue, crushing, grinding, sieving with a 150-300 mesh sieve, and calcining at 700-900 ℃ for 1.5-3 h to obtain pretreated coal gangue;
(2) preparation of Fe3+An iron salt aqueous solution with an ion concentration of 0.4 mol/L;
(3) taking 5 mL of the aqueous solution of the ferric salt prepared in the step (2), adding distilled water to a constant volume of 100 mL, adding the pretreated coal gangue obtained in the step (1) into the solution, and magnetically stirring for 1 h;
the aqueous solution of the iron salt is alpha-Fe2O3Mass meter, alpha-Fe2O3The mass ratio of the coal gangue to the pretreated coal gangue is 0.5-5: 100;
(4) adjusting the pH value of the reaction system obtained in the step (3) to 9-11, and then boiling and refluxing for 3 h;
(5) after the processes of suction filtration, washing by distilled water and natural drying, alpha-Fe is obtained2O3A coal gangue composite photocatalyst.
2. The preparation method according to claim 1, wherein in the step (1), the coal gangue is crushed and ground and then is sieved by a 200-mesh sieve, the calcination temperature is 800 ℃, and the calcination time is 2 hours.
3. The method according to claim 1, wherein in the step (2), the iron salt is ferric nitrate, ferric chloride or ferric sulfate.
4. The method according to claim 1, wherein in the step (3), the α -Fe is present2O3The mass ratio of the coal gangue to the pretreated coal gangue is 1-4: 100.
5. The method according to claim 1, wherein in the step (3), the α -Fe is present2O3The mass ratio of the coal gangue to the pretreated coal gangue is 3: 100.
6. The production method according to claim 1, wherein in the step (4), the reaction system has a pH of 10.
7. alpha-Fe prepared by the preparation method of any one of claims 1 to 62O3Application of the coal gangue composite photocatalyst in degradation of chlorophenol compounds.
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| CN115477948A (en) * | 2022-09-22 | 2022-12-16 | 昆明理工大学 | Method for preparing FeOOH modified coal gangue by utilizing red mud |
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