CN111389351A - CuFeO 2/biochar composite magnetic material and preparation method thereof - Google Patents
CuFeO 2/biochar composite magnetic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to CuFeO2A biochar/biochar composite magnetic material is prepared from ginger stalk through carbonizing, and Fe3+Salt and Cu2+Mixing salt in water, continuously adding strong base solution under the condition of stirring, transferring the above-mentioned solution into hydrothermal reaction kettle, making hydrothermal reaction at a certain temperature, naturally cooling the product obtained after hydrothermal reaction, cleaning with deionized water, suction-filtering and drying to constant weight so as to obtain the invented productCuFeO2Biological carbon composite magnetic material. CuFeO obtained by the invention2The biochar composite material has the advantages of large specific surface area, certain magnetism, no additional reducing agent, low cost, short period, high purity and suitability for mass preparation.
Description
Technical Field
The invention belongs to the technical field of biochar preparation, and particularly relates to CuFeO2A biochar composite magnetic material and a preparation method thereof.
Background
CuFeO2The copper-iron ore type oxide is one of delafossite type oxides, consists of Cu and Fe elements which are stored on the earth abundantly and are nontoxic, has a forbidden band width of 1.3-2.1eV, and is often used as a photocatalyst for hydrogen production under visible light, heavy metal reduction in water and organic dye degradation. Further, CuFeO2Redox reaction between bimetallic Fe and Cu (Fe)2+/Fe3+And Cu+/Cu2+) Has synergistic effect on Fenton reaction, Cu+Can catalyze H under a wide pH value2O2OH is generated and Fe is promoted3+The catalyst is also used as a heterogeneous Fenton catalyst to degrade organic pollutants in water. Thus, CuFeO with respect to the delafossite-type structure2Research on material preparation is currently a focus.
Currently, CuFeO is prepared2Common methods for biochar materials include sol-gel methods, solid-phase sintering methods, and hydrothermal methods. Wherein the hydrothermal method does not need sintering, which can avoid the defects of crystal grain growth, easy impurity mixing and the like in the sintering process and can greatly reduce the preparation of CuFeO2Reaction temperature of the biochar material. Hydrothermal synthesis of CuFeO2In the process of biochar, the selected copper sources are all Cu2+Adding a reducing agent in the reaction process to convert the Cu into Cu+The preparation cost is increased, and the method is not favorable for large-scale industrial production. Therefore, how to reduce CuFeO2The preparation cost of the biochar catalyst and the improvement of the catalytic activity of the biochar catalyst become critical problems to be solved urgently.
Disclosure of Invention
Aiming at various defects of the prior art, the inventor researches and designs a CuFeO in long-term practice2Biological carbon composite magnetic material and preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a kind ofCuFeO2A preparation method of biochar/biochar composite magnetic material comprises carbonizing ginger stalks to prepare original ginger stalk biochar and a certain amount of Fe3+Salt and Cu2+Mixing salt in water, continuously adding a strong base solution under the stirring condition, transferring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at a certain temperature, naturally cooling a hydrothermal product, washing with deionized water, carrying out suction filtration, and drying to constant weight to obtain CuFeO2A biochar composite.
Further, the carbonization temperature of the ginger stalks is 300-750 ℃, and the carbonization time is 90 min.
Further, said Fe3+The salt is any one of ferric chloride, ferric nitrate nonahydrate, ferric sulfate or ferric oxalate pentahydrate.
Further, the Cu2+The salt is any one of copper chloride, copper nitrate trihydrate or copper sulfate pentahydrate.
Further, said Fe3+Salt and Cu2+The salt concentration is 10 mmol/L-30 mmol/L.
Further, the strong alkali solution is any one of sodium hydroxide or potassium hydroxide, and the concentration of the strong alkali solution is 50 g/L-80 g/L.
Further, the hydrothermal reaction temperature is 100-200 ℃, and the reaction time is 6-48 hours.
And further, naturally recovering the hydrothermal product to room temperature, washing the hydrothermal product for 2-3 times by using deionized water, performing suction filtration, and finally drying the product after the suction filtration in a blast drying oven at 105 ℃ to constant weight.
CuFeO2The biochar composite magnetic material is prepared by the preparation method, and has large specific surface area and good adsorption effect.
The invention has the beneficial effects that:
the preparation method does not need an additional reducing agent, has low cost, short period and high purity, is suitable for mass preparation and is convenient for industrial production; the obtained CuFeO2The biological carbon composite material improves CuFeO2Compared with pure CuFeO2And biochar, whichThe specific surface area is improved, and the prepared composite material has certain magnetism, so that the composite material has good application prospects in the fields of adsorption, photoelectrocatalysis, advanced oxidation and the like.
Drawings
FIG. 1 is a thermogravimetric analysis diagram of crushed and dried ginger stalks at 30-700 deg.C;
FIG. 2 is a graph showing the yield of ginger stalks at 300, 450, 600 and 750 ℃ carbonization temperatures;
FIG. 3 shows the results of scanning electron microscopy of biochar and its magnetic composite;
FIG. 4 shows CuFeO under different preparation conditions2XRD pattern of biochar;
FIG. 5 is CuFeO2XPS spectra of biochar.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be further described with reference to the following preferred embodiments.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in experimental or practical applications, the materials and methods are described below. In case of conflict, the present specification, including definitions, will control, and the materials, methods, and examples are illustrative only and not intended to be limiting.
The biochar has obvious influence on the volume weight of the red soil, and can effectively improve the water content and the total amount of particles of the soil with lower fertility. The biochar can not only adjust the pH of the soil and increase the organic matters of the soil, but also obviously enhance the NH of the soil by the large specific surface area and the large negative charges on the surface4 +、NO3 -. The absorption of nutrients such as organic phosphorus and the like improves the soil fertility preserving capability. Physical adsorption is generated between the biochar and heavy metal ions, and ion exchange adsorption can also be generated on the surface of the biochar.
The ginger belongs to the Zingiberaceae plant, the origin is India, and the ginger is introduced into European and American areas, and the planting history of the ginger in China is long and the variety is more. Wherein, per 100g of ginger, the water content is removed, the dry matter content accounts for 13.2-15.5g, the soluble saccharide accounts for 2.02-5.35g, the cellulose accounts for 5.23-5.95g, the lipid accounts for 5.7-14.5g, the protein accounts for 7.98-10.04g, the starch accounts for 5.78-8.86g, and the vitamin C accounts for 1.84-3.34 mg.
The ginger stalks are rich in carbon and oxygen elements, wherein the content of the carbon elements accounts for more than half of the content of the carbon elements, so that the ginger stalks are good raw materials for preparing the charcoal.
Example 1:
CuFeO2The preparation method of the biochar composite magnetic material comprises the following steps:
weighing 10 mmol/L Cu (NO) at room temperature according to the Fe: Cu molar ratio of 1:13)2·3H2O and Fe (NO)3)3·9H2Dissolving O in 60ml of deionized water, carrying out ultrasonic treatment for 5-10 minutes until the solid is completely dissolved, adding 1.0g of original ginger stalk charcoal into the solution, adding 50 g/L g of NaOH which plays a role of a mineralizer, continuously stirring for about 10 minutes until the solid is completely dissolved, transferring the mixed solution to a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a homogeneous reactor for hydrothermal reaction, reacting for 12 hours at 160 ℃, cleaning for 2-3 times by using deionized water after the reaction is finished, and drying the product after the filtration in a blast drying oven at 105 ℃ until the weight is constant to obtain a reaction product.
The preparation method of the original ginger stalk biochar comprises the following steps: firstly, naturally dried ginger stalks are taken, washed by water, dried at the temperature of 101 ℃, crushed and sieved by a 100-mesh sieve; setting the initial temperature to be 0 ℃, controlling the heating rate to be 5 ℃/min, staying for 90min at the carbonization temperature of 300 ℃, then adopting a natural cooling mode, after the temperature is recovered to the room temperature, washing for 2 times by using water, drying, grinding by using a mortar and sieving by using a 100-mesh sieve to obtain the original ginger stalk biochar.
Example 2:
CuFeO2The preparation method of the biochar composite magnetic material comprises the following steps:
weighing 30 mmol/L Cu (NO) at room temperature according to Fe: Cu molar ratio of 1:13)2·3H2O and Fe (NO)3)3·9H2Dissolving O in 60ml of deionized water, carrying out ultrasonic treatment for 5-10 minutes until the solid is completely dissolved, adding 1.0g of original ginger stalk charcoal into the solution, adding 80 g/L g of NaOH which plays a role of a mineralizer, continuously stirring for about 20 minutes until the solid is completely dissolved, transferring the mixed solution to a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a homogeneous reactor for hydrothermal reaction for 6 hours at the temperature of 100 ℃, after the reaction is finished, naturally returning the hydrothermal product to room temperature, washing the hydrothermal product with deionized water for 2-3 times, carrying out suction filtration, and finally drying the suction-filtered product in a blowing drying box at the temperature of 105 ℃ until the weight is constant to obtain a reaction product.
The preparation method of the original ginger stalk biochar comprises the following steps: firstly, naturally dried ginger stalks are taken, washed by water, dried at the temperature of 101 ℃, crushed and sieved by a 100-mesh sieve; setting the initial temperature to be 0 ℃, controlling the heating rate to be 5 ℃/min, staying for 90min at the carbonization temperature of 750 ℃, then adopting a natural cooling mode, after the temperature is recovered to the room temperature, washing for 2 times by using water, drying, grinding by using a mortar and sieving by using a 100-mesh sieve to obtain the original ginger stalk biochar.
Example 3:
CuFeO2The preparation method of the biochar composite magnetic material comprises the following steps:
weighing 20 mmol/L Cu (NO) at room temperature according to Fe: Cu molar ratio of 1:13)2·3H2O and Fe (NO)3)3·9H2Dissolving O in 60ml of deionized water, carrying out ultrasonic treatment for 5-10 minutes until the solid is completely dissolved, adding 1.0g of original ginger stalk biochar into the solution, adding 65 g/L of potassium hydroxide which plays a role of a mineralizer, continuously stirring for about 10 minutes until the solid is completely dissolved, transferring the mixed solution to a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a phase-equalizing reactor for hydrothermal reaction, reacting for 48 hours at the temperature of 200 ℃, finishing the reaction, naturally returning the hydrothermal product to the room temperature, washing with deionized water for 2-3 times, carrying out suction filtration, and finally placing the product after suction filtration into a blast drying box at the temperature of 105 DEG CDrying to constant weight to obtain reaction product.
The preparation method of the original ginger stalk biochar comprises the following steps: firstly, naturally dried ginger stalks are taken, washed by water, dried at the temperature of 101 ℃, crushed and sieved by a 100-mesh sieve; setting the initial temperature to be 0 ℃, controlling the heating rate to be 5 ℃/min, staying for 90min at the carbonization temperature of 600 ℃, then adopting a natural cooling mode, after the temperature is recovered to the room temperature, washing for 2 times by using water, drying, grinding by using a mortar and sieving by using a 100-mesh sieve to obtain the original ginger stalk biochar.
Example 4
CuFeO2The preparation method of the biochar composite magnetic material comprises the following steps:
weighing 10 mmol/L Cu (NO) at room temperature according to the Fe: Cu molar ratio of 1:13)2·3H2O and Fe (NO)3)3·9H2Dissolving O in 60ml of deionized water, carrying out ultrasonic treatment for 5-10 minutes until the solid is completely dissolved, adding 1.0g of original ginger stalk charcoal into the solution, adding 75 g/L g of NaOH which plays a role of a mineralizer, continuously stirring for about 20 minutes until the solid is completely dissolved, transferring the mixed solution to a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a homogeneous reactor for hydrothermal reaction, reacting for 12 hours at 160 ℃, cleaning for 2-3 times by using deionized water after the reaction is finished, and drying the product after the hydrothermal reaction in a blast drying oven at 105 ℃ until the weight is constant to obtain a reaction product.
The preparation method of the original ginger stalk biochar comprises the following steps: firstly, naturally dried ginger stalks are taken, washed by water, dried at the temperature of 101 ℃, crushed and sieved by a 100-mesh sieve; setting the initial temperature to be 0 ℃, controlling the heating rate to be 5 ℃/min, staying for 90min at the carbonization temperature of 450 ℃, then adopting a natural cooling mode, after the temperature is recovered to the room temperature, washing for 2 times by using water, drying, grinding by using a mortar and sieving by using a 100-mesh sieve to obtain the original ginger stalk biochar.
Example 5
Pure CuFeO2The preparation method comprises the following steps: at room temperature as Fe: weighing Cu at a molar ratio of 1:115 mmol/L Cu (NO)3)2·3H2O and Fe (NO)3)3·9H2Dissolving O in 70ml of deionized water, carrying out ultrasonic treatment for 5-10 minutes until the solid is completely dissolved, adding 5ml of ethylene glycol into the solution to serve as a reducing agent, adding 70 g/L NaOH which plays a role of a mineralizer, continuously stirring for about 10-15 minutes until the solid is completely dissolved to form a hydrothermal reaction precursor, transferring the hydrothermal reaction precursor to a hydrothermal reaction kettle, carrying out hydrothermal reaction in a homogeneous reactor, reacting for 20 hours at the temperature of 180 ℃, cooling the reaction kettle to room temperature after the reaction, carrying out centrifugal washing on a hydrothermal product sequentially through absolute ethyl alcohol, 0.5 mol/L of nitric acid and deionized water until the hydrothermal reaction precursor is neutral, and drying the centrifugal product in an oven at the temperature of 80 ℃ for 10 hours to obtain pure CuFeO2A material.
Example 6
Thermogravimetric analysis of ginger stalk
Thermogravimetric analysis is carried out on the crushed and dried ginger stalks at the temperature of 30-700 ℃, and the test result is shown in figure 1. The results of calculating the yield of the ginger stalks at the carbonization temperatures of 300 ℃, 450 ℃, 600 ℃ and 750 ℃ are shown in fig. 2.
As can be seen from FIG. 1, the ginger stalk carbonization process is mainly carried out in three stages. Firstly, in the drying stage, at about 100 ℃, the water in the ginger stalks absorbs heat, at the moment, the enthalpy value is 3.50, the weight loss of the sample is 0.48mg, and the weight loss rate is 4.84%. As the temperature increased, the sample entered the volatile pyrolysis stage, at which point the extrapolated onset temperature was 223.13 ℃, the weight loss was 6.30mg, and the weight loss rate was 63.36%. At the moment, the internal thermal decomposition reaction of the main ginger stalks, the rearrangement and the breakage of most chemical bonds occur, a large amount of organic matters volatilize, and the curve II shows that the stage is an exothermic reaction, the enthalpy value is 33.15, because the volatilized gaseous organic matters undergo static osmotic diffusion combustion under the anoxic condition, and heat is provided for the volatilization of the organic matters to support the decomposition. The last stage is a full-area carbonization stage, and the curve I shows that the weight loss rate of the ginger stalks begins to increase when the temperature is 393.18 ℃, the extrapolated termination point temperature is 450 ℃, the weight loss amount is 2.75mg, the weight loss rate is 27.65%, the curve II shows that the heat release process is carried out, the enthalpy value is 35.84, the enthalpy is obviously higher than that of the second stage, and the ginger stalks are rapidly decomposed to generate combustible gases such as tar, acetic acid and the like and methane and the like. The quality of the ginger stalks is not changed along with the rise of the temperature, so that the temperature of 450 ℃ is the lowest complete carbonization temperature of the ginger stalks, and the carbonization temperatures of 300 ℃, 450 ℃, 600 ℃ and 750 ℃ are selected in the test respectively.
As can be seen from fig. 2, when the carbonization temperature is 300 ℃, the yield is the highest, and can reach 46.7%, and when the carbonization temperature is 750 ℃, the yield is only 28.1%, when the temperature is lower, the organic matter in the organic matter is not completely carbonized, and the product is a mixture of incompletely carbonized organic carbon and highly carbonized organic carbon, which belongs to "rubbery" charcoal, but as the carbonization temperature increases, the content ratio of the highly carbonized organic carbon increases, and the charcoal gradually transitions to "glassy" carbon. The raw carbon retention in biochar was found to be very considerable, and in particular the raw carbon retention was closely related to the precursor material of biochar. In the temperature rising process, a large amount of organic matters volatilize to form porous matters, so that the yield of the biochar is reduced as the carbonization temperature for preparing the biochar is increased.
Example 7
CuFeO2Morphology analysis of biochar
The results of scanning electron microscopy of biochar and its magnetic composite are shown in FIG. 3, CuFeO2The EDS of the biochar is shown in FIG. 4. As can be seen from (a) and (b) in fig. 3, under the same magnification (5000 times), the biochar made of the ginger stalks with the carbonization temperature of 450 ℃ is larger in particle size and keeps the original shape better, while the biochar made of the ginger stalks with the carbonization temperature of 600 ℃ is smaller in particle size and larger in specific surface area due to the fact that the biochar is higher in carbonization temperature and less in residual organic matters, and the original components are damaged to a great extent.
As can be seen from (a) and (c), under the load of CuFeO2Then, more crystals in an ellipsoid shape are formed on the surface of the biochar, and the crystals may be CuFeO2Crystals with a large amount of supported crystals when observed from the surfaceThe effect is better, and the adsorption effect is probably better. As can be seen from (c) and (d), CuFeO was adjusted2CuFeO on the surface of the biochar after the adding ratio of the biochar to the biochar is changed from 2:1 to 1:52The density is obviously reduced, the adsorption synergistic effect of the two is possibly weakened, and the adsorption effect is poor. Microscopically, CuFeO2The ellipsoidal shape of the film is formed by a large amount of flaky CuFeO2The experiment adopts a hydrothermal method to prepare CuFeO2The oxidation-reduction reaction time is longer, and the uniform ellipsoidal CuFeO is formed2Good conditions of (1).
Example 8
CuFeO2Crystal structure analysis of biochar
XRD patterns of samples under different preparation conditions are shown in FIG. 4, and CuFeO exists in the samples2(JSPF No.75-2146) and Fe2O3(JSPF No. 89-0599). CuFeO prepared by different doping ratios2CuFeO in biochar2From the obvious difference, when the doping ratio is 5:1, CuFeO2The characteristic peak of (A) is not obvious, but follows CuFeO2Increased doping ratio, CuFeO2The characteristic peak of (a) becomes gradually apparent. CuFeO prepared from biochar with different carbonization temperatures2CuFeO in/BC2The characteristic peak of the copper-iron alloy is also different, the characteristic peak at the carbonization temperature of 450 ℃ is obviously superior to the characteristic peak at the carbonization temperature of 600 ℃, and CuFeO2The more pronounced the synergistic effect with biochar may be, the better the adsorption effect may be.
Example 9
CuFeO2XPS analysis of biochar
For further exploring CuFeO2Chemical composition of/BC surface and valence state of each element to CuFeO2XPS spectrum analysis of biochar showed the results in FIG. 5.
XPS spectrum results show that CuFeO2The biochar contains Cu, Fe, C, O and other elements, and is corrected by 284.6eV of standard binding energy of carbon elements, wherein the binding energy of O1s at the peak position is near 531eV, the binding energy of C1s at the peak position is near 287eV, and both elements are CuFeO2Basic elements in/BC.The characteristic peaks of Cu element appear at 934.7eV (Cu2 p)3/2) And 953.3eV (Cu2 p)1/2) In the vicinity, the difference between the two binding energies was 18.6 eV. The characteristic peaks of Fe respectively appear at 711.25eV (Fe2 p)3/2) And 724eV (Fe2 p)1/2) In the vicinity, the difference between the binding energies was 12.75eV, and it was confirmed that CuFeO may be contained in the sample2The atomic number of Cu element is 29, its projected auger line is L MM series, its electron layer for generating initial hole and electron layer for filling initial hole are respectively L layer and M layer, and the electron layer for emitting auger electron is M layer, and its Cu element can exist two valence states, i.e. Cu element1+And Cu2+And the test result further verifies CuFeO2Is present.
The above detailed description is only for the preferred embodiment of the present invention, and should not be construed as limiting the scope of the invention, i.e., all equivalent variations and modifications within the scope of the present application should be covered by the present invention.
Claims (9)
1. CuFeO2The preparation method of the biochar composite magnetic material is characterized in that the original ginger stalk biochar prepared by carbonizing ginger stalks and a certain amount of Fe3+Salt and Cu2+Mixing salt in water, continuously adding a strong base solution under the stirring condition, transferring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at a certain temperature, naturally cooling a hydrothermal product, washing with deionized water, carrying out suction filtration, and drying to constant weight to obtain CuFeO2A biochar composite material.
2. CuFeO according to claim 12The preparation method of the biochar composite magnetic material is characterized in that the ginger stalk carbonization temperature is 300-750 ℃, and the carbonization time is 90 min.
3. CuFeO according to claim 12The preparation method of the biochar composite magnetic material is characterized in that Fe3+The salt is ferric chloride, ferric nitrate nonahydrate, and sulfuric acidIron or iron oxalate pentahydrate.
4. CuFeO according to claim 32The preparation method of the/biochar composite magnetic material is characterized in that the Cu2+The salt is any one of copper chloride, copper nitrate trihydrate or copper sulfate pentahydrate.
5. CuFeO according to claim 42The preparation method of the biochar composite magnetic material is characterized in that Fe3+Salt and Cu2+The salt concentration is 10 mmol/L-30 mmol/L.
6. CuFeO according to claim 12The preparation method of the biochar composite magnetic material is characterized in that the strong alkali solution is any one of sodium hydroxide or potassium hydroxide, and the concentration of the strong alkali solution is 50 g/L-80 g/L.
7. CuFeO according to claim 12The preparation method of the biochar composite magnetic material is characterized in that the hydrothermal reaction temperature is 100-200 ℃, and the reaction time is 6-48 hours.
8. CuFeO according to claim 72The preparation method of the biological carbon composite magnetic material is characterized in that a hydrothermal product naturally returns to room temperature, is washed for 2-3 times by deionized water and is filtered again, and finally the filtered product is dried in a blast drying oven at 105 ℃ to constant weight.
9. CuFeO2The/biochar composite magnetic material is characterized by being prepared by the preparation method according to any one of claims 1 to 8, and being large in specific surface area and good in adsorption effect.
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| CN113406220A (en) * | 2021-05-24 | 2021-09-17 | 杭州电子科技大学 | Application of magnetic straw biochar and GC/MS (gas chromatography/mass spectrometry) in determination of trace organic phosphorus in complex sample |
| CN114054059A (en) * | 2021-12-15 | 2022-02-18 | 陈雪文 | Method for degrading sulfamethoxazole in wastewater by activating persulfate through magnetic two-dimensional Mxene/CuFeO2 catalyst |
| CN114887624A (en) * | 2022-05-20 | 2022-08-12 | 北京化工大学 | Biochar-loaded bimetal composite catalytic material and preparation method and application thereof |
| CN115634664A (en) * | 2022-11-30 | 2023-01-24 | 广东工业大学 | Preparation method of iron-copper modified biochar composite adsorbent and application of iron-copper modified biochar composite adsorbent in water treatment |
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| CN113406220A (en) * | 2021-05-24 | 2021-09-17 | 杭州电子科技大学 | Application of magnetic straw biochar and GC/MS (gas chromatography/mass spectrometry) in determination of trace organic phosphorus in complex sample |
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| CN115634664A (en) * | 2022-11-30 | 2023-01-24 | 广东工业大学 | Preparation method of iron-copper modified biochar composite adsorbent and application of iron-copper modified biochar composite adsorbent in water treatment |
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