阅读说明：本技术 含铁氧化物@zif-9-67复合材料及其制备、应用 (Iron-containing oxide @ ZIF-9-67 composite material and preparation and application thereof ) 是由 陈新 谌凯 高文忠 陈传明 孙焕运 朱晓伍 于 2020-05-28 设计创作，主要内容包括：本发明公开了一种含铁氧化物@ZIF-9-67复合材料的制备方法,其特征在于,以含铁氧化物为核心,采用ZIF-9-67对含铁氧化物进行包覆；含铁氧化物为Fe<Sub>3</Sub>O<Sub>4</Sub>或Cu<Sub>0.5</Sub>Zn<Sub>0.5</Sub>Fe<Sub>2</Sub>O<Sub>4</Sub>；采用水热法或研磨方式将ZIF-9-67包覆在含铁氧化物表面。本发明采用含铁氧化物@ZIF-9-67复合材料作为催化剂,对苯甲醇和罗丹明B具有选择性催化,反应后不产生有害的废液、废气,无需对废液、废气进行处理,对环境污染较小,同时苯甲醇被催化后产品中唯一的副产物为苯甲酸,使产品精制较为简单,节约产品成本。(The invention discloses a preparation method of an iron-containing oxide @ ZIF-9-67 composite material, which is characterized in that the iron-containing oxide is taken as a core, and the ZIF-9-67 is adopted to coat the iron-containing oxide; the iron-containing oxide is Fe 3 O 4 Or Cu 0.5 Zn 0.5 Fe 2 O 4 (ii) a And coating ZIF-9-67 on the surface of the iron-containing oxide by a hydrothermal method or a grinding method. The invention adopts the iron-containing oxide @ ZIF-9-67 composite material as the catalyst, has selective catalysis on the benzyl alcohol and the rhodamine B, does not generate harmful waste liquid and waste gas after reaction, does not need to treat the waste liquid and the waste gas, has less environmental pollution, and simultaneously has the unique byproduct of benzoic acid in the product after the benzyl alcohol is catalyzed, so that the product is relatively simple to refine, and the product cost is saved.)

1. The preparation method of the iron-containing oxide @ ZIF-9-67 composite material is characterized in that the iron-containing oxide is taken as a core, and the ZIF-9-67 is adopted to coat the iron-containing oxide.

2. The method of preparing the iron oxide @ ZIF-9-67 containing composite material of claim 1, wherein the iron oxide is containedThe compound being Fe₃O₄Or Cu_0.5Zn_0.5Fe₂O₄。

3. The method for preparing the iron-containing oxide @ ZIF-9-67 composite material according to claim 1, wherein the ZIF-9-67 is coated on the surface of the iron-containing oxide by a hydrothermal method or a grinding method.

4. The method of preparing the iron oxide @ ZIF-9-67 containing composite material of claim 2 or 3, wherein when the iron oxide is Cu_0.5Zn_0.5Fe₂O₄The hydrothermal method is adopted, and the specific operation is as follows: dissolving benzimidazole and 2-methylimidazole in solvent to obtain solution a, dissolving cobalt salt in solvent to obtain solution b, mixing solution a and solution b, adding Cu_0.5Zn_0.5Fe₂O₄Mixing, carrying out hydrothermal reaction, cooling, centrifuging, washing and drying to obtain Cu_0.5Zn_0.5Fe₂O₄@ ZIF-9-67 composite material;

the hydrothermal reaction is specifically performed as follows: heating the reaction kettle containing the reaction materials to 75-85 ℃, preserving heat for 1.5-2.5h, then heating to 130-140 ℃, and preserving heat for 34-38 h.

5. The method for preparing the iron oxide @ ZIF-9-67-containing composite material according to claim 4, wherein the molar ratio of the benzimidazole to the 2-methylimidazole to the cobalt salt is 1: 1: 1, benzimidazole and Cu_0.5Zn_0.5Fe₂O₄The mass ratio of (A) to (B) is 0.2-0.5: 0.45-0.55; the cobalt salt is cobalt chloride, cobalt bromide, cobalt nitrate or cobalt sulfate.

6. The method of preparing the iron oxide @ ZIF-9-67 containing composite material of claim 2 or 3, wherein when the iron oxide is Cu_0.5Zn_0.5Fe₂O₄The grinding mode is adopted, and the specific operation is as follows: mixing Cu_0.5Zn_0.5Fe₂O₄Grinding with ZIF-9-67 to obtain Cu_0.5Zn_0.5Fe₂O₄@ ZIF-9-67 composite material.

7. The method of preparing the iron oxide @ ZIF-9-67 containing composite material of claim 2 or 3, wherein when the iron oxide is Fe₃O₄The hydrothermal method is adopted, and the specific operation is as follows: mixing Fe₃O₄Grinding with ZIF-9-67 to obtain Fe₃O₄@ ZIF-9-67 composite material.

8. The method of preparing the iron oxide @ ZIF-9-67 containing composite material of claim 7, wherein Fe₃O₄And ZIF-9-67 in a mass ratio of 90-92: 80-85.

9. An iron-containing oxide @ ZIF-9-67 composite material, characterized in that it is obtained by the process for the preparation of an iron-containing oxide @ ZIF-9-67 composite material as claimed in any one of claims 1 to 8.

10. The use of the iron oxide @ ZIF-9-67 containing composite material of claim 9 as a catalyst.

Technical Field

The invention relates to the technical field of catalysts, and particularly relates to an iron-containing oxide @ ZIF-9-67 composite material, and a preparation method and application thereof.

Background

Benzaldehyde is the simplest aromatic aldehyde, also known as benzoic acid. Benzaldehyde can be subjected to various reactions such as hydrogenation, condensation, disproportionation and the like. So the benzaldehyde can be used as an intermediate for synthesizing various fine chemical products. At present, the industrial production method of benzaldehyde is a toluene chlorination hydrolysis method, but the waste liquid treatment of the method needs to be solved, a large amount of hydrogen chloride generated in the reaction process is easy to corrode equipment and pipelines, the material requirement is high, the prepared product contains chlorine, the product cannot be directly applied to synthesis of medicines and spices, a product refining work section needs to be added, and the product cost is increased.

The iron-containing oxide includes a ferrite material and an oxide of iron. The ferrite material is spinel-type, has excellent magnetic properties and other excellent properties, and is widely applied in life or industry, wherein copper-zinc ferrite as an important ferrite material is firstly developed by Japan and is produced in large quantities in the middle of the 30 th century in 20 th century, and has important application in wave absorption, storage and catalysis. And Fe₃O₄As an oxide of iron, the iron has a crystal structure of cubic inverse spinel at normal temperature, has good conductivity, andthe magnetic material has magnetism at normal temperature, can be attracted by a magnet, has great application in industry, also has catalytic performance and has potential wide application prospect.

ZIF-9-67 is a novel zeolite imidazole metal framework molecular sieve, which also has a certain catalytic action but poor catalytic performance. A new catalyst is searched, the advantages of the iron-containing oxide and the ZIF-9-67 can be integrated, the selective catalytic reaction can be carried out, toxic and harmful gas and liquid are not generated during the reaction, and the environmental pollution is less.

Disclosure of Invention

The invention aims to solve the defects in the prior art, and provides an iron-containing oxide @ ZIF-9-67 composite material and a preparation method and application thereof.

A preparation method of an iron-containing oxide @ ZIF-9-67 composite material takes the iron-containing oxide as a core, and the ZIF-9-67 is adopted to coat the iron-containing oxide.

Preferably, the iron-containing oxide is Fe₃O₄Or Cu_0.5Zn_0.5Fe₂O₄。

Fe₃O₄The reference documents are: zhang Gift pine, functional Fe₃O₄Preparation of magnetic microspheres and application study in environmental protection [ D]Preparation and modification of nano ferroferric oxide and influence of magnetic field [ D ] of university of Shanxi Shi, 2014 and Song Qing Feng]North river university, 2008.

Fe₃O₄The preparation method comprises the following steps: 0.3434g of ferric chloride hexahydrate is put in a mortar and ground into a powder state; adding powdered ferric trichloride hexahydrate, 1.4982g sodium acetate trihydrate and 0.2899g polyethylene glycol-4000 into 10mL of ethylene glycol for multiple times, stirring in a magnetic stirrer for 80min, slowly dissolving pale yellow solid, changing the white color of the solution into reddish brown, transferring the obtained reddish brown solution into a 50mL reaction kettle, heating the reaction kettle to 200 ℃ from room temperature in an incubator, keeping the temperature of the oven unchanged to enable the reaction solution to react at 200 ℃ for 8h, taking out the reaction kettle, naturally cooling to room temperature at room temperature, and repeatedly using a mixed solution of ethanol and distilled waterWashing for 4 times, drying the filtrate in a 60 deg.C oven to obtain powder solid, i.e. Fe₃O₄。

Fe₃O₄The preparation method also comprises the following steps: slowly adding 0.4367g ferric chloride hexahydrate into a mixed solution consisting of 76mL of ethylene glycol and 4mL of ethylenediamine for multiple times, stirring for 30min under the action of a magnetic stirrer, basically completely dissolving a light yellow solid, transferring the mixed solution into a 100mL high-pressure reaction kettle, putting the reaction kettle into a constant-temperature drying box, heating from room temperature to 150 ℃, keeping the temperature for 24h, taking out the reaction kettle, naturally cooling to room temperature, washing the obtained mixed system with absolute ethyl alcohol, centrifuging, putting the mixed system into a 60 ℃ drying box, drying to obtain a solid, putting the solid into a muffle furnace which is filled with nitrogen at 450 ℃ (the heating rate of 10 ℃/min), and sintering for 2h to obtain a black magnetic solid, namely Fe₃O₄。

Cu_0.5Zn_0.5Fe₂O₄The preparation method comprises the following steps: dissolving ferric trichloride hexahydrate, copper chloride dihydrate and anhydrous zinc chloride slowly and gradually in 60mL of ethylene glycol, stirring for 20min, adding sodium acetate trihydrate and polyethylene glycol after the ferric trichloride hexahydrate, the copper chloride dihydrate and the anhydrous zinc chloride are completely dissolved, pouring the mixture into a 100mL polytetrafluoroethylene stainless steel reaction kettle, putting the reaction kettle into a drying box at 200 ℃ for reacting for 8h (counting time when the temperature of the drying box reaches 200 ℃), naturally cooling to room temperature, and repeatedly centrifuging at high speed to obtain a blackish brown product, namely Cu_0.5Zn_0.5Fe₂O₄。

The dosage of the raw materials is as follows:

	first group	Second group
			Ferric chloride hexahydrate	1.072g	1.712g
Cupric chloride dihydrate	0.338g	0.342g
			Anhydrous zinc chloride	0.2704g	0.2740g
Sodium acetate trihydrate	7.5g	7.38g
			Polyethylene glycol	1.4g	1.51g

Cu_0.5Zn_0.5Fe₂O₄The preparation method comprises the following steps: adding deionized water into 1.61g of ferric trichloride, 0.67g of copper chloride and 0.99g of zinc nitrate (the zinc nitrate should be excessive by 5%), placing the mixture on a magnetic stirrer, and adding magnetons to stir and dissolve the mixture; weighing 5g of sodium hydroxide to prepare a 10% sodium hydroxide solution, adjusting the pH value to 12 by using the sodium hydroxide solution after the mixture is completely dissolved, continuously stirring for 30 minutes, slowly pouring the solution into a polytetrafluoroethylene high-pressure reaction kettle with the filling degree of the reaction kettle being 78-82%, putting the reaction kettle into an electric heating constant-temperature air blowing drying oven, and reacting for 8 hours at 200 ℃; taking out the reaction kettle from the oven, opening the reaction kettle after the temperature is reduced properly, taking out the inner container of the reaction kettle, cooling the reaction solution to room temperature, pouring the product into a centrifuge tube after cooling, placing the centrifuge tube into a centrifuge for centrifugation, and pouring the centrifuged supernatant liquid into the reaction kettleRepeatedly cleaning and centrifuging the powder obtained at the bottom of the waste liquid pool for 4-5 times by using deionized water and absolute ethyl alcohol, and drying in an oven at 80 ℃ to obtain Cu_0.5Zn_0.5Fe₂O₄And (3) powder.

Preferably, the ZIF-9-67 is coated on the surface of the iron-containing oxide by a hydrothermal method or a grinding method.

Preferably, when the iron oxide is Cu_0.5Zn_0.5Fe₂O₄The hydrothermal method is adopted, and the specific operation is as follows: dissolving benzimidazole and 2-methylimidazole in solvent to obtain solution a, dissolving cobalt salt in solvent to obtain solution b, mixing solution a and solution b, adding Cu_0.5Zn_0.5Fe₂O₄Mixing, carrying out hydrothermal reaction, cooling, centrifuging, washing and drying to obtain Cu_0.5Zn_0.5Fe₂O₄@ ZIF-9-67 composite material;

the hydrothermal reaction is specifically performed as follows: heating the reaction kettle containing the reaction materials to 75-85 ℃, preserving heat for 1.5-2.5h, then heating to 130-140 ℃, and preserving heat for 34-38 h.

Preferably, the molar ratio of benzimidazole, 2-methylimidazole and cobalt salt is 1: 1: 1, benzimidazole and Cu_0.5Zn_0.5Fe₂O₄The mass ratio of (A) to (B) is 0.2-0.5: 0.45-0.55; the cobalt salt is cobalt chloride, cobalt bromide, cobalt nitrate or cobalt sulfate.

Preferably, when the iron oxide is Cu_0.5Zn_0.5Fe₂O₄The grinding mode is adopted, and the specific operation is as follows: mixing Cu_0.5Zn_0.5Fe₂O₄Grinding with ZIF-9-67 to obtain Cu_0.5Zn_0.5Fe₂O₄@ ZIF-9-67 composite material.

Preferably, when the iron oxide is Fe₃O₄The hydrothermal method is adopted, and the specific operation is as follows: mixing Fe₃O₄Grinding with ZIF-9-67 to obtain Fe₃O₄@ ZIF-9-67 composite material.

Preferably, Fe₃O₄And ZIF-9-67 in a mass ratio of 90-92: 80-85.

ZIF-9-67 references are: a preparation of a novel ZIF-9-67 membrane and its study on the gas separation performance of CO2 [ D ]. university of beijing chemical industry, 2014.

The ZIF-9-67 is prepared by adopting the following process: dissolving cobalt nitrate in 30mL of N, N-dimethylformamide, stirring for 30min, dissolving benzimidazole and 2-methylimidazole in 30mL of N, N-dimethylformamide, stirring for 30min, and uniformly mixing the two solutions after complete dissolution to obtain a purple solution; pouring the solution into a 100mL polytetrafluoroethylene stainless steel reaction kettle, and placing the reaction kettle in an electric heating constant-temperature air blowing drying oven with the temperature kept at 135 ℃ for 48 hours; centrifuging at high speed for 3-4 times to obtain purple product; the product was then washed with methanol (methanol was added and the methanol was sealed with a preservative film to prevent evaporation of methanol) for 24h, and the process was repeated for 7 days, and the product was dried in a vacuum oven at 60 ℃ for 48 h.

ZIF-9-67 is also prepared by the following process: respectively and slowly adding benzimidazole and 2-methylimidazole for multiple times into 30mL of N, N-dimethylformamide to dissolve solid powder completely, slowly adding cobalt nitrate for multiple times into 30mL of N, N-dimethylformamide to stir continuously until the solid is dissolved, mixing the two solutions, and mixing under the action of a magnetic stirrer to ensure that the two solutions are completely fused and stirred continuously for 20 min; transferring the mixed solution into a reaction kettle, placing the reaction kettle containing the mixed solution into an oven, heating the mixed solution from room temperature to 80 ℃, then reacting for 2 hours, further heating the mixed solution to 135 ℃, then reacting for 36 hours, taking out the reaction kettle, cooling the reaction kettle to room temperature, opening the reaction kettle, taking out the reaction mixed solution, performing suction filtration by using a vacuum pump to obtain a solid, collecting a purple product on the surface of the filter paper, washing by using ethanol, performing suction filtration again to obtain a purple solid, pouring fresh absolute methanol to soak for 24 hours, performing suction filtration, collecting the purple solid, replacing the fresh absolute methanol to soak for 24 hours, repeating the steps for 5 times, centrifuging by using a centrifuge to obtain a solid, washing by using ethanol, placing the solid in a constant-temperature drying box at 80 ℃ to dry for 36 hours at constant temperature, and obtaining the purple solid which is ZIF-9.

In the practical operation process, the cobalt nitrate hexahydrate is often selected.

The preparation process of the ZIF-9-67 adopts the following raw materials in amount:

	first group	Second group	Third group
				Cobalt nitrate hexahydrate	0.6424g	0.6396g	0.6487g
2-methylimidazole	0.1698g	0.1679g	0.1617g
				Benzimidazole compounds	0.2336g	0.2379g	0.2306g

The iron-containing oxide @ ZIF-9-67 composite material is prepared by adopting the preparation method of the iron-containing oxide @ ZIF-9-67 composite material.

The iron-containing oxide @ ZIF-9-67 composite material is applied as a catalyst.

Preferably, the iron oxide @ ZIF-9-67-containing composite material is used for catalyzing and oxidizing benzyl alcohol.

Preferably, the iron-containing oxide @ ZIF-9-67 composite material is applied to catalytic degradation of rhodamine B.

The invention adopts the iron-containing oxide @ ZIF-9-67 composite material as the catalyst, has selective catalysis on the benzyl alcohol and the rhodamine B, does not generate harmful waste liquid and waste gas after reaction, does not need to treat the waste liquid and the waste gas, has less environmental pollution, and simultaneously has the unique byproduct of benzoic acid in the product after the benzyl alcohol is catalyzed, so that the product is relatively simple to refine, and the product cost is saved.

Drawings

FIG. 1 shows Fe obtained in example 2₃O₄XRD pattern of (a).

FIG. 2 is an XRD pattern of ZIF-9-67 obtained in example 2.

FIG. 3 shows Fe obtained in example 2₃O₄An infrared spectrum of (1).

FIG. 4 shows Fe obtained in example 2₃O₄The ultraviolet spectrogram of the solution obtained after the catalytic degradation of rhodamine B by illumination of the @ ZIF-9-67 composite material is an ultraviolet spectrum curve with no illumination, natural illumination for 10min, natural illumination for 20min, natural illumination for 30min, natural illumination for 40min, natural illumination for 50min, natural illumination for 60min and natural illumination for 70min sequentially from top to bottom in the figure.

FIG. 5 shows Cu obtained in examples 3 and 4_0.5Zn_0.5Fe₂Infrared spectrum of O, wherein 1 is Cu obtained in example 3_0.5Zn_0.5Fe₂IR spectrum curve of O, 2 is Cu obtained in example 4_0.5Zn_0.5Fe₂Infrared spectral curve of O.

FIG. 6 shows Cu obtained in examples 3 and 4_0.5Zn_0.5Fe₂XRD pattern of O, wherein 1 is Cu obtained in example 3_0.5Zn_0.5Fe₂XRD profile of O, 2 is Cu obtained in example 4_0.5Zn_0.5Fe₂XRD profile of O.

FIG. 7 is an infrared spectrum of ZIF-9-67 obtained in example 3 and example 4, wherein 1 is an infrared spectrum curve of ZIF-9-67 obtained in example 3, and 2 is an infrared spectrum curve of ZIF-9-67 obtained in example 4.

FIG. 8 is an XRD pattern of ZIF-9-67 obtained in example 4, wherein 1 is an XRD pattern of ZIF-9-67 obtained in example 3, and 2 is an XRD pattern of ZIF-9-67 obtained in example 4.

FIG. 9 shows Cu obtained in example 4_0.5Zn_0.5Fe₂O₄The ultraviolet spectrogram of the solution obtained after the catalytic degradation of rhodamine B by illumination of the @ ZIF-9-67 composite material is an absorbance curve with no illumination, natural illumination for 10min, natural illumination for 20min, natural illumination for 30min, natural illumination for 40min, natural illumination for 50min, natural illumination for 60min and natural illumination for 70min sequentially from top to bottom.

FIG. 10 shows Cu obtained in example 5_0.5Zn_0.5Fe₂Infrared spectrum of O.

FIG. 11 shows Cu obtained in example 5_0.5Zn_0.5Fe₂O₄XRD pattern of (a).

FIG. 12 shows Cu obtained in example 5_0.5Zn_0.5Fe₂O₄@ ZIF-9-67 Infrared Spectroscopy of the composite material.

FIG. 13 shows Cu obtained in example 5_0.5Zn_0.5Fe₂O₄@ ZIF-9-67 XRD pattern of the composite material.

FIG. 14 is a gas chromatogram of a mixed standard stock solution of benzyl alcohol, benzaldehyde, and benzoic acid at a concentration of 1.0 g/L.

FIG. 15 shows Cu obtained in example 5_0.5Zn_0.5Fe₂O₄Gas chromatogram of the solution obtained after catalytic oxidation of benzyl alcohol by the @ ZIF-9-67 composite material.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples.