CN115430428A - Biochar supported iron cluster catalyst and preparation method thereof - Google Patents
Biochar supported iron cluster catalyst and preparation method thereof Download PDFInfo
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- CN115430428A CN115430428A CN202211242303.5A CN202211242303A CN115430428A CN 115430428 A CN115430428 A CN 115430428A CN 202211242303 A CN202211242303 A CN 202211242303A CN 115430428 A CN115430428 A CN 115430428A
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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
- 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
- B01J23/80—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 zinc, cadmium or mercury
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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
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
Abstract
The invention relates to the technical field of organophosphorus pesticide wastewater treatment, in particular to a biochar loaded iron cluster catalyst and a preparation method thereof, specifically adding zinc nitrate hexahydrate and ferrous nitrate hexahydrate into a biochar dispersion system, and adding a dimethyl imidazole methanol solution after stirring to prepare a precursor; soaking the precursor in a mixed solution of methanol and ammonia water to obtain C @ Zn/Fe-ZIF; calcining C @ Zn/Fe-ZIF in a nitrogen atmosphere to obtain the biochar supported iron cluster catalyst. The biochar supported iron cluster catalyst takes the biochar as a carbon-based material, and enables iron cluster atoms to be stably dispersed on the carbon-based material, and has the catalytic efficiency and the micro-scale of equivalent monoatomicThe catalyst can be used for efficiently activating H 2 O 2 The method not only can effectively degrade the organic phosphorus, but also can reduce the toxicity of the water body, and obviously improves the treatment effect of the organic phosphorus pesticide wastewater.
Description
Technical Field
The invention relates to the technical field of organophosphorus pesticide wastewater treatment, in particular to a biochar loaded iron cluster catalyst and a preparation method thereof.
Background
Organic phosphorus accounts for nearly 34% of agricultural production and sale pesticides worldwide, and in China, organic phosphorus pesticides account for more than 80% of pesticide markets. Organophosphorus pesticides are not only various but also are toxic substances which are difficult to dispose, and the excessive use of the organophosphorus pesticides can cause serious pollution to the ecological environment and can generate chain reaction on agricultural yield and productivity. In addition, the long-term exposure to the high-concentration organophosphorus pesticide environment can cause endocrine metabolism disorder, even can cause a series of harms to the growth and development of children, reproductive function and other systems, and can induce the generation of various cancer cells. Because the organic matter content in the organophosphorus pesticide wastewater is high, the chemical components are complex and the harmfulness is large, the organophosphorus pesticide wastewater cannot directly enter a conventional biochemical treatment system and needs to be effectively pretreated.
The fenton method uses hydrogen peroxide as an oxidant to oxidize ferrous ions into ferric ions and generate hydroxyl radicals, and the generated radicals can attack organophosphorus pesticides to generate intermediate products with low toxicity or no toxicity. The traditional Fenton method is based on the reaction of ferrous sulfate and hydrogen peroxide, and although the Fenton method has strong catalytic oxidation efficiency, the combination of hydrogen peroxide and ferrous sulfate can only generate free radicals, and coexisting ions in sewage have great interference on the free radicals, so that the defect of poor oxidation effect exists. In addition, the two medicaments of hydrogen peroxide and ferrous sulfate are used together, so that the cost is high, and the generated sludge amount is large. When the proportion of the Fenton chemical is not appropriate, the iron ion content is too high, so that the water quality is colored again, and secondary pollution is caused.
Compared with free radicals, non-free radicals have the following characteristics: 1. the non-free radicals can not generate secondary free radicals, so that the oxidation process is not obviously influenced by coexisting substances in water; 2. the non-free radical oxidation process does not oxidize halogen ions to form ClO 3 - Or BrO 3 - (ii) a 3. The non-radical oxidation process does not consume too much hydrogen peroxide and metal activator.
Carbon-based catalysts are widely studied for their large specific surface area, special pore structure, abundant functional groups and defect sites. It is believed that defects at the edges of the structure and oxygen-containing functional groups can activate hydrogen peroxide to generate non-free radicals. The biochar is used as a stable carbon carrier, and due to the excellent electrochemical performance and the regular morphological arrangement of the biochar, the biochar is well researched in electrocatalysis, and meanwhile, the catalytic performance of the biochar is greatly improved due to the loading of a carbon-based material and metal.
Various biochar-supported iron-based catalysts have been developed to abate Fe 3+ /Fe 2+ While maintaining H 2 O 2 High efficiency of activation. Carbonaceous materials are an ideal support because they do not contain metals and have a high surface area. Fe reduction by dispersing iron on carbonaceous materials by chemical bonding 3+ /Fe 2+ And provides an unconventional electron distribution, thereby enhancing long-term catalytic activity. While dispersed loading can mitigate active site aggregation to a large extent, maximizing active site exposure remains a significant challenge.
The monatomic catalyst has a more stable active site due to a larger dispersibility, and therefore, the monatomic catalyst anchored on a suitable carrier has a strong prospect. However, in the water treatment industry, especially for the degradation of PPCPs, the use of monatomic catalysts as pollutant degradation catalysts can significantly increase their application costs. Despite the strong catalytic efficacy of monatomic catalysts, the complex preparation process and low yields make them challenging to apply in practice.
The invention is provided in view of the above.
Disclosure of Invention
The invention aims to provide a biochar supported iron cluster catalyst and a preparation method thereof, wherein the catalyst has good stability and reusability, and H activated by the catalyst 2 O 2 The organic phosphorus can be effectively degraded, the toxicity of the water body can be reduced, and the treatment effect of the organic phosphorus pesticide wastewater is obviously improved.
The invention provides a preparation method of a biochar loaded iron cluster catalyst, which comprises the following steps:
adding zinc nitrate hexahydrate and ferrous nitrate hexahydrate into a dispersion system of the biochar, stirring, and adding a methanol solution of dimethyl imidazole to prepare a precursor; soaking the precursor in a mixed solution of methanol and ammonia water to obtain C @ Zn/Fe-ZIF; calcining C @ Zn/Fe-ZIF in a nitrogen atmosphere to obtain the biochar supported iron cluster catalyst.
According to the invention, the biological carbon is coated with ZIF, so that the biological carbon forms carbon structures of different forms after being calcined, and stable attachment sites can be provided for single atoms, so that iron atom clusters are not excessively aggregated, and the catalytic efficiency of the biological carbon is increased. Meanwhile, zn is directly lost after high-temperature calcination, the biochar is etched in the loss process, the specific surface area of the biochar is increased, and Fe with an activation function is remained in the biochar. That is, the whole system is changed into biological carbon loaded iron atom cluster by calcination, the whole structure is changed, and the main substances after calcination are carbon and atomic iron and a small amount of nitrogen element. The calcination step must be carried out in a nitrogen atmosphere in order to carbonize the product directly, and if calcination is carried out in oxygen, the product is oxidized to produce biochar and Fe in atomic form.
The precursor of C @ Zn/Fe-ZIF is prepared by compounding zinc nitrate hexahydrate and ferrous nitrate hexahydrate, impurities are not easy to introduce, a small amount of N element can be introduced into nitrate radicals to increase the catalytic efficiency, and Zn can etch biochar in the process of loss after high-temperature calcination, so that the specific surface area of the biochar is increased.
The biochar loaded iron cluster catalyst prepared by the invention disperses iron atoms on a carbonaceous material in a chemical combination mode, thereby reducing Fe 3+ /Fe 2+ The leaching solves the problem of secondary pollution, and Fe is in an atomic state, exposes more active sites and is H 2 O 2 The activation of the catalyst provides unconventional electron distribution, and an activation system taking singlet oxygen non-free radicals as main components is formed, so that the long-term catalytic activity is improved, and organic pollutants such as organic phosphorus and the like which are difficult to degrade and persistent organic pollutants are effectively removed.
The specific use ratio of the biochar, the zinc nitrate hexahydrate, the ferrous nitrate hexahydrate and the dimethyl imidazole is not strictly limited, but in order to obtain the optimal catalytic effect, the mass ratio of the biochar, the zinc nitrate hexahydrate, the ferrous nitrate hexahydrate and the dimethyl imidazole is (4-6): (0.2-3): (0.1-3): (4-6), and not less than 1g of ferrous nitrate hexahydrate is matched with each 1g of zinc nitrate hexahydrate.
In the invention, in order to improve the dispersibility of the biochar and ensure that the iron-based atoms can be uniformly loaded on the surface of the biochar, anhydrous methanol is required to be used for dispersing, and other organic solvents such as anhydrous ethanol, DMSO, NMP and the like can be added in a proper amount. The dispersion system of the biochar in the invention is an anhydrous methanol solution of the biochar;
specifically, grinding the biochar, adding the biochar into anhydrous methanol, and performing ultrasonic dispersion to obtain a biochar dispersion system; and in the dispersion system, the dosage of the biochar and the absolute methanol is 4-6mL per 1g of biochar corresponding to the volume of the absolute methanol.
Preferably, the technical scheme is that zinc nitrate hexahydrate and ferrous nitrate hexahydrate are added into a dispersion system of the biochar, the mixture is stirred for not less than 10min, a methanol solution of dimethyl imidazole is added, the mixture is stirred vigorously for not less than 1h, and a precursor is prepared after centrifugal washing; wherein the time for vigorous stirring is specifically 1.5-2.5h.
The use ratio of the precursor to the mixed solution of methanol and ammonia water is not strictly limited, so as to ensure that the precursor is completely soaked, specifically, the volume of the mixed solution of methanol and ammonia water corresponding to each 1g of the precursor is 8-12mL, and preferably 10mL, wherein the volume ratio of methanol to ammonia water is 2.
The precursor is soaked in the mixed solution of methanol and ammonia water for 20-26h.
In order to ensure that the C @ Zn/Fe-ZIF polymer is directly carbonized, nitrogen atmosphere is selected during calcination, the temperature is controlled to be 800-1000 ℃, and the time is 1.5-2.5h.
Preferably, the biochar is prepared from agricultural wastes; and the agricultural waste comprises any one or more of walnut shells, bagasse, corncobs, pine nut shells, straws and hot pepper straws.
The biochar supported iron cluster catalyst prepared by the method also belongs to the protection scope of the invention.
The preparation method of the biochar supported iron cluster catalyst has at least the following technical effects:
1. according to the biochar loaded iron cluster catalyst, the biochar is used as a carbon-based material, organic phosphorus can be effectively degraded, and the iron clusters are stably dispersed on the carbon-based material, so that the catalyst has equivalent monatomic catalytic efficiency and trace iron leaching;
2. the charcoal-supported iron cluster catalyst can efficiently activate H 2 O 2 Allowing activated H to stand 2 O 2 The method has high removal rate of various pollutants in the water body and high practical value;
3. the biochar supported iron cluster catalyst has good stability and reusability, and H activated by the catalyst 2 O 2 The organic phosphorus can be effectively degraded, the toxicity of the water body can be reduced, and the treatment effect of the organic phosphorus pesticide wastewater is obviously improved;
4. in the preparation process of the invention, the preparation liquid can be recycled, thus greatly reducing the production cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM image of biochar used in the present invention;
FIG. 2 is an SEM image of a biochar-supported iron cluster catalyst prepared in example 1 of the present invention;
FIG. 3 is a graph of the effect of catalyst loading on contaminant degradation according to the present invention;
FIG. 4 shows a schematic view of the present invention H 2 O 2 The effect of dose on contaminant degradation;
FIG. 5 shows coexistence of anion Cl in the present invention - Impact on contaminant degradation;
FIG. 6 shows coexisting anion NO of the present invention 3 - Impact on contaminant degradation;
FIG. 7 shows coexisting anions H according to the present invention 2 PO 4 - Impact on contaminant degradation;
FIG. 8 shows coexistence of anionic HCO according to the present invention 3 - The impact on the degradation of contaminants;
FIG. 9 illustrates the effect of different water bodies on contaminant degradation according to the present invention;
FIG. 10 shows the degradation of different contaminants by the catalyst of the present invention;
FIG. 11 shows the effect of the catalysts prepared in example 1, comparative example 1 and comparative example 2 of the present invention on the degradation of contaminants;
FIG. 12 shows the effect of the catalysts prepared in examples 1, 3 and 4 of the present invention on the degradation of contaminants.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The biochar used in the embodiment of the invention is mainly prepared from walnut shell waste, and specifically comprises the following steps:
taking a plurality of walnut shells, drying the walnut shells in an oven at 45 ℃ for 24h, then crushing the walnut shells in a crusher, sieving the walnut shells with a 100-mesh sieve, calcining the sieved powder in a tube furnace in a nitrogen atmosphere at 700 ℃ (the heating speed is 5 ℃/min) for 2h to obtain biochar, and cooling and packaging the biochar for later use.
Example 1
S11, grinding 5g of biochar, adding the biochar into 25mL of anhydrous methanol solution, and performing ultrasonic dispersion to obtain a biochar dispersion system;
s12, adding 2g of Zn (NO) into the biochar dispersion system 3 ) 2 ·6H 2 O and 3g Fe (NO) 3 ) 2 ·6H 2 O, stirring for 15min, adding 5g of a methanol solution of dimethylimidazole, stirring vigorously for 2h, centrifuging and washing to obtain a precursor;
s13, putting the precursor obtained in the step (2) into a mixed solution of methanol and ammonia water (the volume ratio of the methanol to the ammonia water is 2;
and S14, calcining the material obtained in the step (3) in a nitrogen atmosphere at the temperature of 900 ℃ for 2 hours to obtain the biochar loaded iron cluster catalyst.
Example 2
S21, grinding 4g of biochar, adding the biochar into 16mL of anhydrous methanol solution, and performing ultrasonic dispersion to obtain a biochar dispersion system;
s22, adding 1g of Zn (NO) into the biochar dispersion system 3 ) 2 ·6H 2 O and 1g Fe (NO) 3 ) 2 ·6H 2 O, stirring for 10min, adding a methanol solution of 5g of dimethyl imidazole, stirring vigorously for 1.5h, centrifuging and washing to obtain a precursor;
s23, putting the precursor obtained in the step (2) into a mixed solution of methanol and ammonia water (the volume ratio of the methanol to the ammonia water is 2;
and S24, calcining the material obtained in the step (3) in a nitrogen atmosphere at 800 ℃ for 2.5 hours to obtain the biochar supported iron cluster catalyst.
Example 3
S31, grinding 6g of biochar, adding the biochar into 36mL of anhydrous methanol solution, and performing ultrasonic dispersion to obtain a biochar dispersion system;
s32, adding 2g of Zn (NO) into the biochar dispersion system 3 ) 2 ·6H 2 O and 3g Fe (NO) 3 ) 2 ·6H 2 O, stirring for 20min, adding 5g of a methanol solution of dimethylimidazole, stirring vigorously for 2.5h, centrifuging and washing to obtain a precursor;
s33, putting the precursor obtained in the step (2) into a mixed solution of methanol and ammonia water (the volume ratio of the methanol to the ammonia water is 2;
and S34, calcining the material obtained in the step (3) in a nitrogen atmosphere at the temperature of 1000 ℃ for 1.5h to obtain the biochar loaded iron cluster catalyst.
Fig. 1 and fig. 2 are the microstructure diagrams of biochar and biochar supported iron cluster catalyst, respectively, and comparing fig. 1-2, it can be seen that the biochar successfully supports iron cluster and is distributed relatively uniformly.
Comparative example 1
ZnCl is selected 2 ·3H 2 O instead of Zn (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 2 ·6H 2 And O is used in combination, and other steps and parameters are the same as those of the example 1.
Comparative example 2
Selecting ZnSO 4 ·7H 2 O instead of Zn (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 2 ·6H 2 And O is compounded for use, and other steps and parameters are the same as those of the example 1.
Comparative example 3
Selecting Co (NO) 3 ) 2 ·6H 2 Substitution of O for Fe (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 And O is used in combination, and other steps and parameters are the same as those of the example 1.
Comparative example 4
Selecting Cu (NO) 3 ) 2 ·3H 2 Substitution of O for Fe (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 And O is compounded for use, and other steps and parameters are the same as those of the example 1.
In order to verify the effect of the catalyst prepared in example 1 of the present invention, a thiophosphoric acid ester (methyl parathion) was selected as a target pollutant.
First, the amount of catalyst used and H were investigated 2 O 2 The influence of the dosage on the target pollutants in the water body can be seen from FIG. 3 when H 2 O 2 The dosage is 0.2mM, and when the dosage of the catalyst is changed from 50mg/L to 100mg/L, the degradation of target pollutants in the water body is not obviously influenced, and the degradation effect of nearly 95 percent to 100 percent can be achieved within 20 min. Similarly, as can be seen from FIG. 4, when the amount of the catalyst is 50mg/L, H is 2 O 2 When the dosage is changed within 0.2-0.4mM, the degradation of target pollutants in the water body is not obviously influenced, and the degradation effect of nearly 95-100 percent can be achieved within 20 min.
Meanwhile, the invention also researches the influence of coexisting anions on the whole catalytic reaction system, and the combined graph of 5-8 shows that except HCO 3 - In addition, other coexisting anions Cl - 、NO 3 - And H 2 PO 4 - Has no obvious influence on the whole reaction system, and HCO 3 - The influence is large probably because it affects the pH of the entire reaction system.
Thus, the biochar supported iron cluster catalyst of the invention activates H 2 O 2 Then, the singlet oxygen non-free radicals generated in the system can not generate secondary free radicals, namely the oxidation process of the singlet oxygen non-free radicals is not obviously influenced by coexisting substances in water; does not oxidize halogen ions to form ClO 3 - Or BrO 3 - Causing secondary pollution to the water body; finally, excessive hydrogen peroxide and metal activator are not consumed, and H contained in the effluent water 2 O 2 Can be repeatedly used.
In order to further research the influence of the water body on the reaction system, ultrapure water, tap water, river water and sewage are selected for experiments. As can be seen from fig. 9, the degradation efficiency of the target contaminants in tap water and river water almost approaches that of ultrapure water; the degradation rate constant using sewage as background is significantly reduced. The possible reason is that certain levels of ions (phosphate and bicarbonate) and natural organic matters exist in the water, but the removal rate of organic pollutants by the reaction system can be basically kept at about 90 percent within 30 min.
Finally, the invention researches the degradation effect of the reaction system on different pollutants, and specifically selects five pollutants with different functional groups, such as Nitenpyram (NTP), imidacloprid (ICP), thiacloprid (TCP), carbamazepine (CBZ) and Atrazine (ATZ), to carry out degradation research. As can be seen from FIG. 10, the degradation efficiency of the reaction system to CBZ, ATZ, NTP, ICP and TCP can reach 100% within 30min, thus demonstrating that the catalyst of the present invention has broad spectrum.
The ZIF coated charcoal is a basis capable of providing stable attachment points for single atoms, and C @ Zn/Fe-ZIF in the preparation process can form carbon structures in different forms after calcination, so that stable attachment points are provided for the single atoms, and iron atom clusters cannot be excessively aggregated, and the catalytic efficiency of the catalyst is remarkably improved. Therefore, the present invention performed comparative experiments on the preparation of ZIF materials, as shown in comparative examples 1-4.
As can be seen from FIG. 11, znCl was selected 2 ·3H 2 O or ZnSO 4 ·7H 2 O instead of Zn (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 2 ·6H 2 O is compounded and used, and the prepared catalyst activates H 2 O 2 The effect of degrading the thiophosphoric acid esters (methyl parathion) is much lower than that of the catalyst prepared in example 1 of the present invention because Zn (NO) is selected 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 2 ·6H 2 And when the O is compounded for preparing the ZIF material, zn can be gasified and etched to form biochar during high-temperature burning, and nitrate radicals can not introduce impurities. As shown in FIG. 12, fe is relative to H, compared to Cu and Co (harmful heavy metals) 2 O 2 The activation effect of the catalyst is optimal, the degradation effect on organic phosphorus is obvious, and secondary pollution to the environment cannot be caused even if a small amount of Fe is leached out.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the biochar supported iron cluster catalyst is characterized by comprising the following steps of:
adding zinc nitrate hexahydrate and ferrous nitrate hexahydrate into a dispersion system of the biochar, stirring, and adding a methanol solution of dimethyl imidazole to prepare a precursor; soaking the precursor in a mixed solution of methanol and ammonia water to obtain C @ Zn/Fe-ZIF; calcining the C @ Zn/Fe-ZIF in a nitrogen atmosphere to obtain the biochar supported iron cluster catalyst.
2. The method according to claim 1, wherein the mass ratio of the biochar, the zinc nitrate hexahydrate, the ferrous nitrate hexahydrate and the dimethylimidazole is (4-6): (0.2-3): (0.1-3): (4-6).
3. The method for preparing according to claim 1, wherein the dispersion of biochar is an anhydrous methanol solution of biochar;
preferably, the biochar is ground, added into anhydrous methanol and subjected to ultrasonic dispersion to obtain a biochar dispersion system;
preferably, the volume of anhydrous methanol per 1g of biochar is 4-6mL.
4. The preparation method according to claim 1, characterized in that zinc nitrate hexahydrate and ferrous nitrate hexahydrate are added into a biochar dispersion system and stirred for not less than 10min, a methanol solution of dimethyl imidazole is added, stirred vigorously for not less than 1h, and after centrifugal washing, a precursor is prepared;
preferably, the period of vigorous stirring is 1.5-2.5h.
5. The method according to claim 1, wherein the volume of the mixed solution of methanol and aqueous ammonia is 8 to 12mL per 1g of the precursor.
6. The production method according to claim 1, wherein the volume ratio of the methanol to the aqueous ammonia is 2.
7. The preparation method according to claim 1, wherein the precursor is soaked in the mixed solution of methanol and ammonia water for 20-26h.
8. The preparation method of claim 1, wherein the calcination is carried out at a temperature of 800-1000 ℃ for 1.5-2.5h.
9. The method according to claim 1, wherein the biochar is produced from agricultural waste;
the agricultural waste comprises any one or more of walnut shells, bagasse, corncobs, pine nut shells, straws and hot pepper straws.
10. A biochar-supported iron cluster catalyst, characterized in that it is prepared by the method of any one of claims 1 to 9.
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