阅读说明：本技术 一种金属氧化物的制备方法及金属氧化物 (Preparation method of metal oxide and metal oxide ) 是由 王峰 张健 王业红 张志鑫 于 2019-11-19 设计创作，主要内容包括：本发明涉及一种金属氧化物的方法。该金属氧化物制备方法为：将可溶性金属盐和二元或多元有机酸,分别分散于有机溶剂后制成一定浓度的母液。在20℃～150℃的合成温度下,在搅拌的条件下,按金属离子/-COOH(有机酸根)为20:1～1:10的摩尔比例,将上述母液混合。反应1h～72h后,转移至压力容器,在20℃～150℃温度下,静置12h～120h。将沉淀物分离、洗涤、干燥,利用金属与有机酸的配位作用,得到氧化物前驱体。将上述氧化物前驱体在500℃～800℃惰性气氛下碳化处理2h～12h；在400℃～550℃氧化气氛中焙烧2h～12h,最终获得氧化物。该类氧化物具有比表面大,有望在催化、吸附等领域存在潜在的应用。(The present invention relates to a method for producing a metal oxide. The preparation method of the metal oxide comprises the following steps: soluble metal salt and binary or polybasic organic acid are respectively dispersed in organic solvent to prepare mother liquor with a certain concentration. Mixing the mother liquor at a synthesis temperature of 20-150 ℃ and under the condition of stirring according to the molar ratio of metal ions/-COOH (organic acid radical) of 20: 1-1: 10. After reacting for 1-72 h, transferring the mixture to a pressure vessel, and standing the mixture for 12-120 h at the temperature of 20-150 ℃. Separating, washing and drying the precipitate, and obtaining an oxide precursor by utilizing the coordination of metal and organic acid. Carbonizing the oxide precursor for 2 to 12 hours at 500 to 800 ℃ under inert atmosphere; roasting for 2-12 h in an oxidizing atmosphere at 400-550 ℃ to finally obtain the oxide. The oxide has large specific surface area, and is expected to have potential application in the fields of catalysis, adsorption and the like.)

1. A method for preparing an oxide. The method is characterized in that:

soluble metal salt and binary and/or polybasic organic acid are used as raw materials, and an oxide precursor is obtained through the coordination of metal and carboxyl; and carbonizing the oxide precursor under inert gas and roasting in oxidizing atmosphere to finally obtain the oxide.

2. The method for producing an oxide according to claim 1, wherein:

the preparation process of the oxide precursor comprises the following steps: respectively dispersing metal salt and binary and/or polybasic organic acid in an organic solvent to prepare a mother solution; mixing the mother liquor at a synthesis temperature of 20-150 ℃ (preferably 80-140 ℃) and under the condition of stirring, wherein the molar ratio of metal ions/COOH (organic acid radical) is 20: 1-1: 10 (preferably 4: 1-1: 4); after reacting for 1-72 h (preferably 12-48 h), transferring to a pressure vessel, and standing for 12-120 h (preferably 24-72 h) at the temperature of 20-150 ℃ (preferably 80-140 ℃); separating, washing and drying the precipitate, and obtaining an oxide precursor by utilizing the coordination of metal and organic acid.

3. The method for producing an oxide according to claim 1 or 2, characterized in that:

the metal salt is nitrate or chloride containing one or more of iron, cobalt, nickel, copper and zinc;

the organic acid is one or more of malonic acid, succinic acid, adipic acid, pimelic acid, terephthalic acid, isophthalic acid and 2, 5-furandicarboxylic acid.

4. The method for producing an oxide according to claim 1, wherein:

the metal salt is preferably one or more of ferric nitrate, nickel nitrate and zinc nitrate;

the organic acid is preferably one or two of terephthalic acid and 2, 5-furandicarboxylic acid.

5. The method for producing an oxide according to claim 1, wherein:

the oxide precursor needs to be carbonized, and the carbonization process comprises the following steps: carbonizing the oxide precursor at 500-800 ℃ in inert atmosphere for 2-12 h;

the inert atmosphere is one or more of nitrogen, argon and helium.

6. The method for producing an oxide according to claim 1, wherein:

the oxide precursor is subjected to carbonization treatment and then oxidation treatment, wherein the oxidation treatment process comprises the following steps: roasting the carbonized oxide precursor for 2-12 h in an oxidizing atmosphere at 400-550 ℃;

the oxidizing atmosphere is one or two of oxygen or air.

7. A metal oxide obtained by the production method as described in any one of claims 1 to 6.

Technical Field

The invention belongs to the technical field of preparation of oxides, and particularly relates to a preparation method of a high-surface oxide.

Background

Metal oxides are common in daily life, and most of the oxides have high thermal stability. Metal oxides have a wide range of applications and can be used as desiccants, catalysts, polishing powders and artificial gemstones, and therefore play an important role in the development of human socioeconomic performance, particularly in the fields of catalysis and adsorption materials. The metal oxide can be used as a main catalyst, a cocatalyst and a carrier to be widely used in catalytic reactions such as oxidation, dehydrogenation, hydrogenation, polymerization, synthesis and the like; in addition, the metal oxide can be used as a non-toxic catalyst for adsorbing water, acid gas or alkaline gas and the like. For metal oxides, the specific surface area is an important parameter, which determines the efficiency of metal oxide utilization. Therefore, the development of a new synthetic method for preparing the high-specific-surface oxide material has very important significance.

Disclosure of Invention

The invention has the significance of providing a novel preparation method of the oxide material with the high specific surface, the method has better universality, can be used for preparing materials such as iron oxide, cobalt oxide, nickel oxide, copper oxide and the like with the high specific surface, and the specific surface is relatively higher and can reach 200m at most²/g。

The oxide material designed by the invention is prepared by the following scheme. Soluble metal salt and binary or polybasic organic acid are taken as raw materials, and an oxide precursor is obtained through the coordination of metal and acid; carbonizing the oxide under inert gas and roasting the oxide in oxidizing atmosphere to finally obtain the oxide, wherein the material has the characteristic of large specific surface, and the specific surface reaches 120-200 m²(ii) in terms of/g. The preparation process of the oxide precursor comprises the following steps: respectively dispersing metal salt and di-or poly-organic acid in an organic solvent to prepare mother liquor with a certain concentration. Mixing the mother liquor at a synthesis temperature of 20-150 ℃ and under the condition of stirring according to the molar ratio of metal ions/-COOH (organic acid radical) of 20: 1-1: 10. After reacting for 1-72 h, transferring the mixture to a pressure vessel, and standing the mixture at the temperature of 20-150 ℃ for 12-eAnd (4) 120 h. Separating, washing and drying the precipitate, and obtaining an oxide precursor by utilizing the coordination of metal and organic acid. The metal salt is nitrate or chloride containing iron, cobalt, nickel, copper and zinc; the organic acid is one or more of malonic acid, succinic acid, adipic acid, pimelic acid, terephthalic acid, isophthalic acid and 2, 5-furandicarboxylic acid. The metal salt is preferably one or more of ferric nitrate, nickel nitrate and zinc nitrate; the organic acid is preferably one or two of terephthalic acid and 2, 5-furandicarboxylic acid. The oxide precursor needs to be carbonized, and the carbonization process comprises the following steps: carbonizing the oxide precursor for 2-12 h at 500-800 ℃ under inert atmosphere; the inert atmosphere is one or more of nitrogen, argon and helium; the oxide precursor is subjected to carbonization treatment and then oxidation treatment, wherein the oxidation treatment process comprises the following steps: roasting the carbonized oxide precursor for 2-12 h in an oxidizing atmosphere at 400-550 ℃; the oxidizing atmosphere is one or two of oxygen or air.

The oxide has large specific surface area, and is expected to have potential application in the fields of catalysis, adsorption and the like.

The specific implementation mode is as follows:

in order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.

Example 1

14.5g of hydrated nickel nitrate and 18g of terephthalic acid are respectively added into an organic solvent of 400mL of N, N-diethylformamide and 5L N, N-diethylformamide for dissolution; after dissolution, the two solutions were mixed at 100 ℃ and stirred for 8.5h to obtain a mother liquor. And putting the mother solution into a reaction bottle, sealing, reacting for 72 hours at the reaction temperature of 140 ℃, taking out, centrifuging, washing and drying to obtain the nickel oxide precursor. Carbonizing the nickel oxide precursor, and treating for 12 hours at 500 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting at 550 deg.C in air for 4h to obtain nickel oxide material with specific surface of 200m²/g。

Example 2

28.6g of nickel chloride hexahydrate and 9.96g of isophthalic acid are respectively added into an organic solvent of 240mL of N-ethylformamide and 60mL of N-ethylformamide for dissolution; after dissolution, the two solutions are mixed at 40 ℃ and stirred for 8 hours to prepare mother liquor. And putting the mother solution into a reaction bottle, sealing, reacting for 48 hours at the reaction temperature of 150 ℃, taking out, centrifuging, washing and drying to obtain the nickel oxide precursor. Carbonizing the nickel oxide precursor, and treating for 24 hours at 750 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting in air at 500 deg.C for 12h to obtain nickel oxide material with specific surface of 180m²/g。

Example 3

62.6g of hydrated zinc nitrate and 4.5g of 2, 5-furandicarboxylic acid are respectively added into an organic solvent of 10L N, N-diethylformamide and 400mL of N, N-diethylformamide for dissolution; after dissolution, the two solutions were mixed at 55 ℃ and stirred for 3h to obtain a mother liquor. And (3) putting the mother solution into a reaction bottle, sealing, reacting for 72 hours at the reaction temperature of 120 ℃, taking out, centrifuging, washing and drying to obtain the zinc oxide precursor. Carbonizing the zinc oxide precursor, and treating for 24 hours at 650 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting at 500 deg.C in air for 12h to obtain zinc oxide material with specific surface area of 145m²/g。

Example 4

Adding 41.2g of hydrated copper nitrate and 48.0g of oxalic acid into organic solvents of 1L N-ethylformamide and 2L N-ethylformamide respectively for dissolving; after dissolution, the two solutions were mixed at 40 ℃ and stirred for 4h to obtain a mother liquor. And putting the mother solution into a reaction bottle, sealing, reacting at the reaction temperature of 130 ℃ for 60 hours, taking out, centrifuging, washing and drying to obtain the copper oxide precursor. Carbonizing the copper oxide precursor, and treating for 24 hours at 700 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting in air at 500 deg.c for 12 hr to obtain copper oxide material,the specific surface area thereof is 131m²/g。

Example 5

96g of hydrated iron nitrate and 23.9g of 2, 5-furandicarboxylic acid were dispersed in 2.5L of 2L N, N-dimethylformamide, respectively, to prepare a mother liquor. The above mother liquors were mixed with stirring at 25 ℃ and reacted for 2.5 hours, and then transferred to a pressure vessel and allowed to stand at 140 ℃ for 48 hours. Separating, washing and drying the precipitate to obtain the ferric oxide precursor. Carbonizing the iron oxide precursor, and treating for 12 hours at 750 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting at 550 deg.C in air for 12h to obtain iron oxide material with specific surface area of 189m²/g。

Example 6

14.5g of hydrated cobalt nitrate and 18g of terephthalic acid are respectively added into an organic solvent of 400mL of N, N-diethylformamide and 5L N, N-diethylformamide for dissolution; after dissolution, the two solutions were mixed at 100 ℃ and stirred for 8.5h to obtain a mother liquor. And (3) putting the mother solution into a reaction bottle, sealing, reacting for 72 hours at the reaction temperature of 140 ℃, taking out, centrifuging, washing and drying to obtain the cobalt oxide precursor. Carbonizing the cobalt oxide precursor, and treating for 4 hours at 800 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting at 550 deg.C in air for 4h to obtain cobalt oxide material with specific surface of 185m²/g。

Example 7

14.5g of hydrated nickel nitrate and 18g of pimelic acid are respectively added into 400mL of organic solvent of N, N-diethylformamide and 5L N, N-diethylformamide for dissolution; after dissolution, the two solutions were mixed at 100 ℃ and stirred for 8.5h to obtain a mother liquor. And putting the mother solution into a reaction bottle, sealing, reacting for 72 hours at the reaction temperature of 140 ℃, taking out, centrifuging, washing and drying to obtain the nickel oxide precursor. Carbonizing the nickel oxide precursor, and treating for 12 hours at 500 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting at 550 deg.C in air for 4h to obtain nickel oxide material with specific surface of 125m²/g。

Example 8

14.5g of hydrated nickel nitrate and 18g of adipic acid are respectively added into an organic solvent of 400mL of N, N-diethylformamide and 5L N, N-diethylformamide for dissolution; after dissolution, the two solutions were mixed at 100 ℃ and stirred for 8.5h to obtain a mother liquor. And putting the mother solution into a reaction bottle, sealing, reacting for 72 hours at the reaction temperature of 140 ℃, taking out, centrifuging, washing and drying to obtain the nickel oxide precursor. Carbonizing the nickel oxide precursor, and treating for 24 hours at 630 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting in air at 500 deg.C for 4h to obtain nickel oxide material with specific surface of 121m²/g。

Example 9

Respectively adding 14.5g of hydrated nickel nitrate and 18g of succinic acid into 400mL of organic solvent of N, N-diethylformamide and 5L N, N-diethylformamide for dissolving; after dissolution, the two solutions were mixed at 100 ℃ and stirred for 8.5h to obtain a mother liquor. And putting the mother solution into a reaction bottle, sealing, reacting for 72 hours at the reaction temperature of 140 ℃, taking out, centrifuging, washing and drying to obtain the nickel oxide precursor. Carbonizing the nickel oxide precursor, and treating for 12 hours at 500 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting at 550 deg.C in air for 4h to obtain nickel oxide material with specific surface of 122m²/g。

Example 10

96g of hydrated nickel nitrate and 23.9g of isophthalic acid were dispersed in 2.5L of 2L N, N-dimethylformamide to prepare a mother liquor. The above mother liquors were mixed with stirring at 25 ℃ and reacted for 2.5 hours, and then transferred to a pressure vessel and allowed to stand at 140 ℃ for 48 hours. And separating, washing and drying the precipitate to obtain the nickel oxide precursor. Carbonizing the nickel oxide precursor, and treating for 12 hours at 500 ℃ under nitrogen; the carbonized material is subjected to oxidation treatment, and the process is as follows: roasting at 550 deg.c in air for 4 hr to obtain nickel oxide material with specific surface area of 194m²/g。