CN110436606B - Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2Preparation method of (1) - Google Patents
Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2Preparation method of (1) Download PDFInfo
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Abstract
Magnetic oxidant MnxZn1‑xFe2O4/δ‑MnO2Belonging to the field of inorganic oxidation materials. The invention firstly prepares the magnetic matrix Mn by a hydrothermal methodxZn1‑xFe2O4Then preparing the magnetic oxidant Mn by an auto-oxidation reduction-hydrothermal methodxZn1‑xFe2O4/δ‑MnO2. The method has the advantages of simple preparation process, less used equipment cost and low energy consumption. Prepared MnxZn1‑xFe2O4/δ‑MnO2The stability is strong, the magnetic separation is convenient, the oxidation activity is high, 0.01g of prepared magnetic oxidant is dispersed in 100mL of 10mg/L rhodamine B solution, and the degradation rate reaches more than 99.4 percent when the pH is 1 and 15 min. The product prepared by the invention can be widely used in the field of oxidative degradation of organic pollutants.
Description
Technical Field
The invention relates to a magnetic oxidant MnxZn1-xFe2O4/δ-MnO2Belonging to the technical field of inorganic oxidation materials.
Background
Manganese dioxide is a transition metal oxide with stable performance, belongs to an n-type semiconductor material, has the characteristics of good catalytic performance, adsorption performance, oxidation performance, excellent electrochemical performance, energy storage, excellent ion exchange performance, environmental friendliness and the like, and simultaneously has the characteristics of large specific surface area, more surface active groups, variable valence states, simple preparation, low production cost (a large amount of manganese exists in soil and minerals), and the like, and the properties and the structure of the manganese dioxide, such as surface appearance, crystallinity, purity and the like, can be regulated and controlled by changing key factors such as temperature, concentration, pH, voltage and the like of a product synthesis reaction, so that the manganese dioxide is widely applied to important fields such as catalysis, adsorption, batteries and the like all the time, and has an important role in the treatment of organic polluted wastewater in the environment. The crystal form of manganese dioxide mainly comprises alpha, beta, gamma, delta, epsilon and the like, and the preparation method mainly comprises a hydrothermal method, an oxidation-reduction method, a thermal decomposition method, an electrodeposition method, a sol-gel method and the like. Manganese dioxide is used as an oxidant and is mainly used for preparing aldehyde by alcohol oxidation, preparing terminal alkyne by reaction of unsaturated enol after oxidation and amine, converting cyano into amide, preparing formamide and diazo compound by amine oxidation, cracking alpha-hydroxy acid, oxidizing diarylmethane, converting diarylketone, converting aldehyde into carboxylic acid, preparing disulfide from sulfur, preparing phosphide from phosphorus or preparing ketone from amine and the like. However, since manganese dioxide is an amphoteric oxide, it has both an oxidizing property and a reducing property, and is mainly controlled by reaction conditions, which results in poor efficiency of manganese dioxide oxidant and is also inconvenient for recycling. At present, no report about the preparation of the magnetic manganese dioxide oxidant is found.
Pure manganese dioxide has poor catalytic performance, and MnO is not limited2The catalyst is also an adsorbent, but the action process and the finished light solid MnO2Suspended in the solution, solid-liquid separation is difficult to realize, recycling is not facilitated, and MnO can be caused2Secondary pollution to the environment, hence to MnO2Compounding with magnetic substances has been in the spotlight of researchers. Such as Synthesis of a Thin-Layer MnO2Nanosheet-Coated Fe3O4MnO prepared from Nanocomponite as a magnetic Separable Photocatalyst2/Fe3O4Although the composite magnetic catalyst can be recycled, the method still has some defects: (1) the composite catalyst has poor treatment effect on pollutants, 0.01g of the composite catalyst degrades 50mL of methylene blue with the concentration of 20mg/L, the degradation rate within 3h is only about 89%, and the effect efficiency on dyes which are difficult to degrade, such as rhodamine B, is not considered; (2) when in catalysis, the participation of light is needed,and the requirement on pH is high, the restriction conditions are too many, and the wide application is not facilitated. Also, for example, in CN 106215948B, "a method for preparing manganese dioxide composite magnetic catalyst" (reference 1), a magnetic matrix manganese zinc ferrite is prepared by a calcination method, and then a co-oxidation reduction method is used to prepare a manganese dioxide composite magnetic catalyst (β -MnO)2/MnxZn1- xFe2O4) And the recycling can be realized. However, this method still has some disadvantages: (1) preparation of manganese zinc ferrite (Mn) by roasting methodxZn1-xFe2O4) The temperature of the reaction is 1200 ℃, the energy consumption is high, and the prepared sample has larger particle size and smaller specific surface area, which is not beneficial to MnxZn1-xFe2O4And beta-MnO2The stability of the compound cannot be ensured due to the sufficient combination of the components; (2) method for preparing beta-MnO by adopting manganese permanganate to oxidize manganese sulfate2Manganese element is not fully utilized, and beta-MnO is caused by the increase of the types of raw materials2The purity is limited, affecting beta-MnO2Activity of (a); (3) the catalytic activity is not high, the 5mg manganese dioxide composite magnetic catalyst degrades 100mL of 10mg/L rhodamine B under the action of hydrogen peroxide, and the degradation rate within 1h is only 93.9%; (4) mn prepared by roasting methodxZn1-xFe2O4Small coercive force, limited magnetic retention capacity and no contribution to MnxZn1-xFe2O4/β-Mn2O2And (4) recycling.
Disclosure of Invention
The invention aims to solve the problems of difficult recovery and low oxidation activity of pure manganese dioxide and provides Mn adoptedxZn1-xFe2O4For MnO2Modifying and magnetizing to raise its oxidizing activity and easy recovery and reuse, and is one kind of magnetic oxidant MnxZn1-xFe2O4/δ-MnO2The preparation method has the advantages of simple preparation process, low production cost, short period and high oxidation activity, is convenient to separate and recover from a liquid phase suspension system through an external magnetic field, and avoids the possible belt of an oxidizing agentSecondary pollution from the coming.
The magnetic oxidant Mn of the inventionxZn1-xFe2O4/δ-MnO2The preparation method comprises the following steps:
(1) magnetic matrix MnxZn1-xFe2O4Preparation of
According to the ratio of ZnO to MnO to Fe2O3The molar ratio is 13.3:32.8:53.9, and proper amount of ZnSO is weighed respectively4·7H2O、 MnSO4·H2O、Fe2(SO4)3Fully dissolving with deionized water to obtain a mixed solution; weighing a proper amount of NaOH to prepare 2mol/L NaOH solution; slowly dripping NaOH solution into the mixed solution under magnetic stirring until a brown flocculent product is generated, quickly dripping the NaOH solution until the pH value of the reaction solution is 13, continuously stirring for 0.5h, transferring the reaction solution into a reaction kettle, carrying out hydrothermal reaction for 5h at 200 ℃, cooling to room temperature after the reaction is finished, washing a sample in a beaker with distilled water and absolute ethyl alcohol for multiple times by utilizing the magnetic attraction force of a magnet, then drying for 12h in a drying box at 70 ℃, and grinding to obtain MnxZn1- xFe2O4Powder samples.
(2) Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2Preparation of
0.5140g of potassium permanganate is weighed, added into 65mL of distilled water, mechanically stirred until the potassium permanganate is completely dissolved, and then 1mL of hydrochloric acid (37 wt%) is slowly dripped, and mechanically stirred uniformly to obtain a potassium permanganate solution; according to MnxZn1-xFe2O4And delta-MnO2According to the mass ratio of 10-30: 100, weighing a proper amount of MnxZn1-xFe2O4Adding the mixed solution into a potassium permanganate solution, mechanically stirring for 30min, transferring the mixed solution into a 100mL hydrothermal reaction kettle, sealing, keeping the temperature of 160 ℃ for reaction for 24h, naturally cooling to room temperature after the reaction is finished, and removing upper-layer liquid; centrifugally washing the solid part with distilled water and absolute ethyl alcohol until the solution is colorless, and then drying in a 70 ℃ oven for 12 hours to obtain the magnetic oxidant MnxZn1-xFe2O4/δ-MnO2。
By adopting the technical scheme, the invention mainly has the following effects:
(1) the magnetic oxidant Mn prepared by the method of the inventionxZn1-xFe2O4/δ-MnO2Has high oxidation activity, 0.01g of prepared magnetic oxidant MnxZn1-xFe2O4/δ-MnO2The rhodamine B dye is dispersed in 100mL of rhodamine B solution with the concentration of 10mg/L, and the degradation rate of RhB reaches 99.4 percent in 15min when the pH value is 1.
(2) The magnetic oxidant Mn prepared by the method of the inventionxZn1-xFe2O4/δ-MnO2Can realize solid-liquid separation and recycling under the action of an external magnetic field.
(3) The invention adopts a hydrothermal-autoxidation method for preparation, and has the advantages of simple preparation operation, less required equipment and low energy consumption.
Drawings
FIG. 1 shows MnxZn1-xFe2O4、δ-MnO2And MnxZn1-xFe2O4δ-MnO2X-ray diffraction pattern of (a).
FIG. 2 shows delta-MnO2And MnxZn1-xFe2O4/δ-MnO2An infrared spectrum of (1).
FIG. 3 shows MnxZn1-xFe2O4/δ-MnO2UV-vis absorbance pattern at degradation pH 1RhB solution.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2The preparation method comprises the following specific steps:
(1) magnetic matrix MnxZn1-xFe2O4Preparation of
According to the ratio of ZnO to MnO to Fe2O3Mole ofThe ratio of 13.3:32.8:53.9, respectively weighing appropriate amount of ZnSO4·7H2O、 MnSO4·H2O、Fe2(SO4)3Fully dissolving with deionized water to obtain a mixed solution; weighing a proper amount of NaOH to prepare 2mol/L NaOH solution; slowly dripping NaOH solution into the mixed solution under magnetic stirring until a brown flocculent product is generated, quickly dripping the NaOH solution until the pH value of the reaction solution is 13, continuously stirring for 0.5h, transferring the reaction solution into a reaction kettle, carrying out hydrothermal reaction for 5h at 200 ℃, cooling to room temperature after the reaction is finished, washing a sample in a beaker with distilled water and absolute ethyl alcohol for multiple times by utilizing the magnetic attraction force of a magnet, then drying for 12h in a drying box at 70 ℃, and grinding to obtain MnxZn1- xFe2O4Powder samples.
(2) Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2Preparation of
0.5140g of potassium permanganate is weighed, added into 65mL of distilled water, mechanically stirred until the potassium permanganate is completely dissolved, and then 1mL of hydrochloric acid (37 wt%) is slowly dripped, and mechanically stirred uniformly to obtain a potassium permanganate solution; according to MnxZn1-xFe2O4And delta-MnO2The mass ratio of 10: 100, weighing proper amount of MnxZn1-xFe2O4Adding the mixed solution into a potassium permanganate solution, mechanically stirring for 30min, transferring the mixed solution into a 100mL hydrothermal reaction kettle, sealing, keeping the temperature of 160 ℃ for reaction for 24h, naturally cooling to room temperature after the reaction is finished, and removing upper-layer liquid; centrifugally washing the solid part with distilled water and absolute ethyl alcohol until the solution is colorless, and then drying in a 70 ℃ oven for 12 hours to obtain the magnetic oxidant MnxZn1-xFe2O4/δ-MnO2。
Example 2
Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2The preparation method comprises the following specific steps:
(1) the same as in (1) in example 1.
(2) Magnetic oxidationAgent MnxZn1-xFe2O4/δ-MnO2Preparation of
0.5140g of potassium permanganate is weighed, added into 65mL of distilled water, mechanically stirred until the potassium permanganate is completely dissolved, and then 1mL of hydrochloric acid (37 wt%) is slowly dripped, and mechanically stirred uniformly to obtain a potassium permanganate solution; according to MnxZn1-xFe2O4And delta-MnO2The mass ratio of Mn to Mn is 20: 100, and a proper amount of Mn is weighedxZn1-xFe2O4Adding the mixed solution into a potassium permanganate solution, mechanically stirring for 30min, transferring the mixed solution into a 100mL hydrothermal reaction kettle, sealing, keeping the temperature of 160 ℃ for reaction for 24h, naturally cooling to room temperature after the reaction is finished, and removing upper-layer liquid; centrifugally washing the solid part with distilled water and absolute ethyl alcohol until the solution is colorless, and then drying in a 70 ℃ oven for 12 hours to obtain the magnetic oxidant MnxZn1-xFe2O4/δ-MnO2。
Example 3
Magnetic oxidant MnxZn1-xFe2O4/BiVO4/δ-MnO2The preparation method comprises the following specific steps:
(1) the same as in (1) in example 1.
(2) Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2Preparation of
0.5140g of potassium permanganate is weighed, added into 65mL of distilled water, mechanically stirred until the potassium permanganate is completely dissolved, and then 1mL of hydrochloric acid (37 wt%) is slowly dripped, and mechanically stirred uniformly to obtain a potassium permanganate solution; according to MnxZn1-xFe2O4And delta-MnO2The mass ratio of the Mn to the Mn is 30: 100, and a proper amount of Mn is weighedxZn1-xFe2O4Adding the mixed solution into a potassium permanganate solution, mechanically stirring for 30min, transferring the mixed solution into a 100mL hydrothermal reaction kettle, sealing, keeping the temperature of 160 ℃ for reaction for 24h, naturally cooling to room temperature after the reaction is finished, and removing upper-layer liquid; centrifugally washing the solid part with distilled water and anhydrous ethanol until the solution is colorless, and drying in a 70 deg.C oven for 12 hr to obtain magnetic oxideAgent MnxZn1-xFe2O4/δ-MnO2。
Results of the experiment
Magnetic oxidant Mn prepared in example 1xZn1-xFe2O4/δ-MnO2The catalytic degradation activity is optimal. For easy comparison, delta-MnO was prepared2And (3) sampling. Delta-MnO2The preparation method of (1) is that Mn is not added in the step (2) of example 1xZn1-xFe2O4。
δ-MnO2、MnxZn1-xFe2O4、MnxZn1-xFe2O4/δ-MnO2The XRD pattern of (A) is shown in figure 1. As can be seen, MnO was prepared2Corresponding to diffraction peaks in PDF card (JCPDS 80-1098), the crystal face indexes are (001), (002), (111) and (311) respectively, which shows that the prepared sample is delta-MnO2(ii) a Prepared MnxZn1-xFe2O4The diffraction peak is matched with PDF card (JCPD 24-7400), stronger diffraction peaks appear at crystal faces (111), (220), (311), (222), (400), (422), (511) and (440), and a sample prepared on the surface is tetragonal crystal form MnxZn1-xFe2O4；MnxZn1-xFe2O4/δ-MnO2Has delta-MnO in the diffraction peak of2And MnxZn1-xFe2O4The diffraction peaks of (1), (002) and (111) correspond to delta-MnO2Corresponding to Mn at (220), (311) (440)xZn1-xFe2O4Diffraction peak of (2) indicating MnxZn1-xFe2O4And delta-MnO2The loading is successful, and the crystal structures and phases of the loaded two are not influenced mutually, thereby ensuring that the Mn isxZn1-xFe2O4/δ-MnO2Magnetic and catalytic properties, magnetic tests show that MnxZn1-xFe2O4Has a saturation magnetization (Ms) of 70.61emu g-1Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2Has a saturation magnetization value of 7.70emu g-1Complex Mn dispersed in aqueous solutionxZn1-xFe2O4/δ-MnO2Can be attracted and collected by the magnet within 10 seconds.
δ-MnO2、MnxZn1-xFe2O4/δ-MnO2The FT-IR spectrum of (A) is shown in FIG. 2. It can be seen that the distance is 3423.78cm-1Is delta-MnO2Stretching vibration peak of structural water molecules and skeleton hydroxyl groups in sample, 1619.24cm-1May be a bending vibration peak of 452.06cm for adsorbing hydroxyl in water-1And 509.04cm-1The peak at (B) corresponds to MnO2A vibrational peak of medium Mn-O bonds; in MnxZn1- xFe2O4/δ-MnO2In the spectrum of (1), 3200-3500 cm-1Is the vibration peak of O-H in the sample, and is 400-600 cm-1Corresponding Fe-O bond or FeO in the range4Vibration peak of chemical bond, wherein the characteristic peak ranges corresponding to Mn-O bond and Fe-O bond functional group are the same, and magnetic oxidant MnxZn1-xFe2O4/δ-MnO2Middle MnxZn1-xFe2O4And delta-MnO2It is possible that both share similar functional groups.
Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2The degradation of RhB is shown in fig. 3. It can be seen that when the pH value of the RhB solution is 1, the degradation rate reaches more than 99.4% in 15 min.
Claims (1)
1. Magnetic oxidant MnxZn1-xFe2O4/δ-MnO2The preparation method comprises the following steps:
(1) magnetic matrix MnxZn1-xFe2O4The preparation of (1): according to the ratio of ZnO to MnO to Fe2O3The molar ratio is 13.3:32.8:53.9, and proper amount of ZnSO is weighed respectively4·7H2O、MnSO4·H2O、Fe2(SO4)3With deionized waterFully dissolving to obtain a mixed solution; weighing a proper amount of NaOH to prepare 2mol/L NaOH solution; slowly dripping NaOH solution into the mixed solution under magnetic stirring until a brown flocculent product is generated, quickly dripping the NaOH solution until the pH value of the reaction solution is 13, continuously stirring for 0.5h, transferring the reaction solution into a reaction kettle, carrying out hydrothermal reaction for 5h at 200 ℃, cooling to room temperature after the reaction is finished, washing a sample in a beaker with distilled water and absolute ethyl alcohol for multiple times by utilizing the magnetic attraction force of a magnet, then drying for 12h in a drying box at 70 ℃, and grinding to obtain MnxZn1-xFe2O4A powder sample;
(2) 0.5140g of potassium permanganate is weighed, added into 65mL of distilled water, mechanically stirred until the potassium permanganate is completely dissolved, and then 1mL of hydrochloric acid (37 wt%) is slowly dripped, and mechanically stirred uniformly to obtain a potassium permanganate solution; according to MnxZn1-xFe2O4And delta-MnO2According to the mass ratio of 10-30: 100, weighing a proper amount of MnxZn1-xFe2O4Adding the mixed solution into a potassium permanganate solution, mechanically stirring for 30min, transferring the mixed solution into a 100mL hydrothermal reaction kettle, sealing, keeping the temperature of 160 ℃ for reaction for 24h, naturally cooling to room temperature after the reaction is finished, and removing upper-layer liquid; centrifugally washing the solid part with distilled water and absolute ethyl alcohol until the solution is colorless, and then drying in a 70 ℃ oven for 12 hours to obtain the magnetic oxidant MnxZn1-xFe2O4/δ-MnO2。
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| CN105688793A (en) * | 2016-01-25 | 2016-06-22 | 华东交通大学 | Preparation method of MnO2-based magnetic nano Fe3O4 heavy metal adsorbing material |
| CN106215948A (en) * | 2016-07-06 | 2016-12-14 | 重庆大学 | A kind of preparation method of manganese dioxide composite magnetic catalyst |
| CN109331836A (en) * | 2018-10-10 | 2019-02-15 | 重庆大学 | It is a kind of to prepare β-Bi2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material |
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| CN105688793A (en) * | 2016-01-25 | 2016-06-22 | 华东交通大学 | Preparation method of MnO2-based magnetic nano Fe3O4 heavy metal adsorbing material |
| CN106215948A (en) * | 2016-07-06 | 2016-12-14 | 重庆大学 | A kind of preparation method of manganese dioxide composite magnetic catalyst |
| CN109331836A (en) * | 2018-10-10 | 2019-02-15 | 重庆大学 | It is a kind of to prepare β-Bi2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material |
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| One-pot synthesis of hierarchical MnO2-modified diatomites for electrochemical capacitor electrodes;Yu Xin Zhang et al.;《Journal of Power Sources》;20140131;第246卷;第450页 * |
| 不同因素下酸性水钠锰矿治理印染废水效果及其机制研究;陈若愚;《中国优秀硕士学位论文全文数据库（工程科技I辑）》;20150331;第12页，第26页 * |
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