CN111185242A - Co3O4-mMOxZIFs composite material and preparation and application thereof - Google Patents
Co3O4-mMOxZIFs composite material and preparation and application thereof Download PDFInfo
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Abstract
The invention particularly relates to Co3O4‑mMOxZIFs composite material and preparation and application thereof. Co of the invention3O4‑mMOxM in the ZIFs composite material is selected from one or more of Cu, Mn, Ce and Zn; m is more than or equal to 0 and less than or equal to 0.1; x is more than or equal to 0.5 and less than or equal to 2. Compared with the existing transition metal oxide catalyst, the composite material of the invention has high catalytic activity, low material cost and good stability, and solves the problem of agglomeration of the metal catalyst on the carrier. In addition, the composite material has a controllable structure, so that a single metal oxide composite material can be obtained, and a bimetal composite material or a multi-metal oxide composite material can be prepared. The preparation method is simple and easy to operate, has low requirements on production conditions, and can be used for large-scale production.
Description
Technical Field
The invention particularly relates to Co3O4-mMOxZIFs composite material and preparation and application thereof.
Background
The problems of air pollution such as haze, acid rain, dust and the like can seriously affect the health of people. Volatile Organic Compounds (VOCs) emitted by industrial activities not only directly affect human health and environmental safety, but also indirectly cause an increase in surface ozone concentration, forming photochemical smog. Therefore, the control of VOCs from the source or the post-treatment of VOCs is of great importance for removing photochemical smog, improving air quality, improving the ecological environment of people and protecting the health of people.
In recent years, technologies for controlling VOCs represented by catalytic combustion have been gradually developed and have made great progress. The catalyst is a core of the catalytic combustion technology and is a key subject of the catalytic combustion technology. The catalyst used for catalytic combustion is mainly divided into a supported noble metal catalyst and a transition metal oxide catalyst, and the two catalysts have obvious effects on the treatment of VOCs. In the prior art, the effect of the supported noble metal catalyst is excellent, but the supported noble metal catalyst is limited by the factors such as the cost, the stability and the like of the catalytic material, and cannot be widely applied. The transition metal oxide catalyst has great advantages in material cost and stability, and becomes the most potential substitute material for noble metal catalyst, wherein the maximum limitation is that a proper carrier needs to be selected, and meanwhile, because the transition metal oxide catalyst is not uniformly dispersed, agglomeration, sintering, carbon deposition and even inactivation easily occur in the calcining process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide Co3O4-mMOxZIFs composite materials. Compared with the existing transition metal oxide catalyst, the composite material of the invention has high catalytic activity, low material cost and good stability, and solves the problem of agglomeration of the metal catalyst on the carrier. In addition, the composite material structure of the present invention mayAnd the single metal oxide composite material can be obtained, and the double metal composite material or the multi-metal oxide composite material can be prepared. The preparation method is simple and easy to operate, has low requirements on production conditions, and can be used for large-scale production.
The invention adopts the following technical scheme:
co3O4-mMOxThe ZIFs composite material, wherein M is selected from one or more of Cu, Mn, Ce and Zn; m is more than or equal to 0 and less than or equal to 0.1; x is more than or equal to 0.5 and less than or equal to 2.
In the present invention, the composite material is Co3O4-mMOx/ZIFs of the formula, wherein Co3O4Is cobalt oxide, MOxAn oxide formed for the M metal; m is the percentage of the total molar weight of Co and M in the composite material; x is related to the oxidation state of the oxide formed by the M metal.
In the present invention, ZIFs are zeolitic imidazolate framework materials (zeolithidazole frameworks). ZIFs are materials with controllable structure, uniform pore size distribution, permanent pores, high specific surface area and high stability, and are used as carriers of catalysts. In the prior art, the transition metal oxide catalyst often cannot be uniformly distributed, so that the problem of agglomeration on a carrier is easy to occur. In the method, the ZIFs material is used as a sacrificial template, the metal/ZIFs material is prepared by controlling the composition of the imidazole ligand and the metal, and then the metal oxide/ZIFs composite material with a special structure can be prepared by regulating and controlling the calcination temperature. The composite material has the greatest advantage that metal is positioned on the framework connection point of the ZIFs, the framework material still keeps the original porous structure in the calcining process, and only the metal is oxidized into metal oxide, so that the transition metal oxide catalyst is uniformly dispersed and is not easy to agglomerate. Meanwhile, the catalyst has higher thermal stability, and can still maintain a porous structure even if calcined at the temperature higher than 500 ℃, so that the catalyst is effectively prevented from being deactivated due to sintering and carbon deposition. In addition, the mixed or composite metal oxide not only has higher catalytic activity than simple metal oxides, but also has better selectivity, thermal stability and poisoning resistance.
Co as described above3O4-mMOxThe preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing imidazole ligand, a Co-containing compound and an M-containing compound in a solvent, reacting at 15-30 ℃ for 100-120 minutes, and standing for 2-10 hours to obtain a Co-M-ZIFs material;
(2) calcining the Co-M-ZIFs material in air atmosphere to obtain Co3O4-mMOxZIFs composite materials.
Preferably, the imidazole ligand is one or two of 2-methylimidazole and imidazole.
Preferably, the Co-containing compound is one or two of cobalt nitrate, cobalt acetate and hydrates thereof.
Further preferably, the Co-containing compound is one or both of cobalt nitrate hexahydrate and cobalt acetate tetrahydrate.
Preferably, the M-containing compound is one or more of copper sulfate, manganese nitrate, manganese acetate, cerium sulfate, cerium nitrate, zinc nitrate and hydrates thereof.
Further preferably, the M-containing compound is one or more of copper sulfate pentahydrate, manganese nitrate tetrahydrate, manganese acetate tetrahydrate, cerium sulfate hexahydrate, cerium nitrate tetrahydrate and zinc nitrate hexahydrate.
Preferably, the solvent is deionized water, ethanol, methanol or dimethylformamide.
Preferably, the imidazole ligand: a Co-containing compound: the molar ratio of the M-containing compounds is 10-4: 1: 0-0.1.
Preferably, the method further comprises the step of carrying out vacuum drying on the Co-M-ZIFs material obtained in the step (1).
Further preferably, the temperature of the vacuum drying is 60-80 ℃ and the time is 10-12 hours.
In the invention, the vacuum drying has two purposes, namely, the purpose of drying is achieved by evaporating the solvent in the reaction process; secondly, volatilizing the solvent in the pore channel to form the porous three-dimensional material. The transition metal in the present invention can be effectively dispersed in the carrier by forming the porous three-dimensional material.
Preferably, the calcination is carried out at a temperature of 300 to 500 ℃ for a time of 3 to 5 hours.
Further preferably, the rate of temperature rise during calcination is controlled to be 10-20 ℃/min.
In the invention, different calcination temperatures can cause weight loss of materials in different degrees, so that the formed materials have differences in properties such as crystal form or specific surface, the crystal form can influence the combination of metal on the surface, and the size of the specific surface can influence the adsorption of VOCs molecules on the surface of the catalyst. The calcining temperature adopted by the invention is 300-500 ℃, and the time is 3-5 hours, so that the material can form the required crystal form and has the optimal catalytic performance.
Co as described above3O4-mMOxThe ZIFs composite material is used as a catalyst.
Further preferably, the Co3O4-mMOxThe ZIFs composite material is used as a catalyst for catalyzing combustion of VOCs.
The invention has the beneficial effects that:
(1) co of the invention3O4-mMOxthe/ZIFs composite material has an adjustable structure, can be a single metal oxide composite material, can also be a double metal oxide composite material or a multi-metal oxide composite material, has a large specific surface area, and is beneficial to the adsorption of VOCs molecules on the surface of a catalyst;
(2) co of the invention3O4-mMOxthe/ZIFs composite material has good catalytic activity in catalyzing combustion of VOCs by serving as a catalyst, can completely catalyze and degrade VOCs by 100% at 240 ℃, and has good stability;
(3) according to the preparation method, Co-M-ZIFs are used as sacrificial templates, metal Co and M in the structure are directly oxidized to generate active components, and the bimetallic oxide catalyst is directly formed in one step, so that the composite characteristic among metal elements can be enhanced, the dispersion degree and the bonding strength of the catalytic active components on the surface of a carrier are improved, and the mechanical strength and the thermal stability of the catalyst are improved;
(4) the preparation method is simple and easy to operate, has low requirements on production conditions, and can be used for large-scale production.
Drawings
FIG. 1 is Co of examples 1 to 53O4-mMOxThe test effect diagram of the/ZIFs composite material for catalyzing the combustion of the toluene.
FIG. 2 is Co of examples 6 to 93O4-mMOxThe test effect diagram of the/ZIFs composite material for catalyzing the combustion of the toluene.
Detailed Description
Example 1
Co3O4The preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing 2-methylimidazole (0.04mol) and cobalt nitrate hexahydrate (0.01mol) in deionized water, reacting at 25 ℃ for 120 minutes, standing for 2 hours to obtain a Co-ZIFs material, and vacuum-drying the Co-ZIFs material at 60 ℃ for 12 hours;
(2) heating to 300 ℃ at a speed of 15 ℃/min in a muffle furnace, and keeping the Co-ZIFs material for 4 hours in an air atmosphere to obtain Co3O4ZIFs composite materials.
Example 2
Co3O4The preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing 2-methylimidazole (0.04mol) and cobalt nitrate hexahydrate (0.01mol) in deionized water, reacting at 25 ℃ for 120 minutes, standing for 2 hours to obtain a Co-ZIFs material, and vacuum-drying the Co-ZIFs material at 60 ℃ for 12 hours;
(2) heating to 350 ℃ at a speed of 15 ℃/min in a muffle furnace, and keeping the Co-ZIFs material for 4 hours in an air atmosphere to obtain Co3O4ZIFs composite materials.
Example 3
Co3O4The preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing 2-methylimidazole (0.04mol) and cobalt nitrate hexahydrate (0.01mol) in deionized water, reacting at 25 ℃ for 120 minutes, standing for 2 hours to obtain a Co-ZIFs material, and vacuum-drying the Co-ZIFs material at 60 ℃ for 12 hours;
(2) heating to 400 ℃ at a speed of 15 ℃/min in a muffle furnace, and keeping the Co-ZIFs material for 4 hours in an air atmosphere to obtain Co3O4ZIFs composite materials.
Example 4
Co3O4-0.1CeO2The preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing 2-methylimidazole (0.04mol), cobalt nitrate hexahydrate (0.009mol) and cerium nitrate tetrahydrate (0.001mol) in deionized water, reacting at 25 ℃ for 120 minutes, standing for 5 hours to obtain a Co-Ce-ZIFs material, and vacuum-drying the Co-Ce-ZIFs material at 60 ℃ for 12 hours;
(2) heating to 400 ℃ at a speed of 15 ℃/min in a muffle furnace, and keeping the Co-Ce-ZIFs material for 4 hours in an air atmosphere to obtain Co3O4-0.1CeO2ZIFs composite materials.
Example 5
Co3O4-0.1MnO2The preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing 2-methylimidazole (0.04mol), cobalt nitrate hexahydrate (0.009mol) and manganese acetate tetrahydrate (0.001mol) in deionized water, reacting at 25 ℃ for 120 minutes, standing for 5 hours to obtain a Co-Mn-ZIFs material, and vacuum-drying the Co-Mn-ZIFs material at 60 ℃ for 12 hours;
(2) heating to 400 ℃ at a speed of 15 ℃/min in a muffle furnace, and keeping the Co-Mn-ZIFs material for 4 hours in an air atmosphere to obtain Co3O4-0.1MnO2ZIFs composite materials.
Example 6
Co3O4-0.01MnO2The preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing 2-methylimidazole (0.04mol), cobalt nitrate hexahydrate (0.0099mol) and manganese acetate tetrahydrate (0.0001mol) in deionized water, reacting at 25 ℃ for 120 minutes, standing for 5 hours to obtain a Co-Mn-ZIFs material, and vacuum-drying the Co-Mn-ZIFs material at 60 ℃ for 12 hours;
(2) in a muffle furnace, at 15 ℃/min literThe temperature is raised to 400 ℃, the Co-Mn-ZIFs material is kept for 4 hours in the air atmosphere, and Co is obtained3O4-0.01MnO2ZIFs composite materials.
Example 7
Co3O4-0.02MnO2The preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing 2-methylimidazole (0.04mol), cobalt nitrate hexahydrate (0.0098mol) and manganese acetate tetrahydrate (0.0002mol) in deionized water, reacting at 25 ℃ for 120 minutes, standing for 5 hours to obtain a Co-Mn-ZIFs material, and vacuum-drying the Co-Mn-ZIFs material at 60 ℃ for 12 hours;
(2) heating to 400 ℃ at a speed of 15 ℃/min in a muffle furnace, and keeping the Co-Mn-ZIFs material for 4 hours in an air atmosphere to obtain Co3O4-0.02MnO2ZIFs composite materials.
Example 8
Co3O4-0.04MnO2The preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing 2-methylimidazole (0.04mol), cobalt nitrate hexahydrate (0.0096mol) and manganese acetate tetrahydrate (0.0004mol) in deionized water, reacting at 25 ℃ for 120 minutes, standing for 5 hours to obtain a Co-Mn-ZIFs material, and vacuum-drying the Co-Mn-ZIFs material at 60 ℃ for 12 hours;
(2) heating to 400 ℃ at a speed of 15 ℃/min in a muffle furnace, and keeping the Co-Mn-ZIFs material for 4 hours in an air atmosphere to obtain Co3O4-0.04MnO2ZIFs composite materials.
Example 9
Co3O4-0.08MnO2The preparation method of the/ZIFs composite material comprises the following steps:
(1) uniformly mixing 2-methylimidazole (0.04mol), cobalt nitrate hexahydrate (0.0092mol) and manganese acetate tetrahydrate (0.0008mol) in deionized water, reacting at 25 ℃ for 120 minutes, standing for 5 hours to obtain a Co-Mn-ZIFs material, and vacuum-drying the Co-Mn-ZIFs material at 60 ℃ for 12 hours;
(2) heating to 400 ℃ at a speed of 15 ℃/min in a muffle furnace, wherein the Co-Mn isKeeping the-ZIFs material in an air atmosphere for 4 hours to obtain Co3O4-0.08MnO2ZIFs composite materials.
Experimental example 1
In the present invention, VOCs are exemplified by toluene. The composite materials obtained in examples 1 to 5 were placed in a quartz tube reactor and subjected to a catalytic toluene combustion activity test. Catalyst activity test conditions: toluene 1000ppm, space velocity 60000 mL/(g.h). The results are shown in FIG. 1.
As can be seen from FIG. 1, the composite material of the present invention can completely burn toluene at 240 ℃, and the degradation rate reaches 100%.
Experimental example 2
Similarly, the catalytic performance of the composite materials with different Mn contents was studied by taking toluene as an example of VOCs. The composite materials obtained in examples 6 to 9 were placed in a quartz tube reactor and subjected to a catalytic toluene combustion activity test. The catalyst activity test conditions were as in experimental example 1. The results are shown in FIG. 2.
As can be seen from FIG. 2, the composite materials with different Mn contents can effectively and completely burn toluene, and the degradation rate reaches 100%.
Claims (10)
1. Co3O4-mMOxThe ZIFs composite material is characterized in that M is selected from one or more of Cu, Mn, Ce and Zn; m is more than or equal to 0 and less than or equal to 0.1; x is more than or equal to 0.5 and less than or equal to 2.
2. Co of claim 13O4-mMOxThe preparation method of the/ZIFs composite material is characterized by comprising the following steps of:
(1) uniformly mixing imidazole ligand, a Co-containing compound and an M-containing compound in a solvent, reacting at 15-30 ℃ for 100-120 minutes, and standing for 2-10 hours to obtain a Co-M-ZIFs material;
(2) calcining the Co-M-ZIFs material in air atmosphere to obtain Co3O4-mMOxZIFs composite materials.
3. Co according to claim 23O4-mMOxThe preparation method of the/ZIFs composite material is characterized in that the imidazole ligand is one or two of 2-methylimidazole and imidazole.
4. Co according to claim 23O4-mMOxThe preparation method of the/ZIFs composite material is characterized in that the Co-containing compound is one or two of cobalt nitrate, cobalt acetate and hydrates thereof.
5. Co according to claim 23O4-mMOxThe preparation method of the/ZIFs composite material is characterized in that the M-containing compound is one or more of copper sulfate, manganese nitrate, manganese acetate, cerium sulfate, cerium nitrate, zinc nitrate and hydrates thereof.
6. Co according to claim 23O4-mMOxThe preparation method of the/ZIFs composite material is characterized in that the solvent is deionized water, ethanol, methanol or dimethylformamide.
7. Co according to claim 23O4-mMOxThe preparation method of the/ZIFs composite material is characterized in that the imidazole ligand: a Co-containing compound: the molar ratio of the M-containing compounds is 10-4: 1: 0-0.1.
8. Co according to claim 23O4-mMOxThe preparation method of the/ZIFs composite material is characterized by further comprising the step of carrying out vacuum drying on the Co-M-ZIFs material obtained in the step (1); the temperature of the vacuum drying is 60-80 ℃, and the time is 10-12 hours.
9. Co according to claim 23O4-mMOxThe preparation method of the/ZIFs composite material is characterized in that the calcining temperature is 300-500 ℃ and the calcining time is 3-5 hours.
10.Co of claim 13O4-mMOxThe ZIFs composite material is used as a catalyst.
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Cited By (3)
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| CN112569927A (en) * | 2020-12-15 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of mesoporous silica-coated cobalt manganese oxide, product and application thereof |
| CN112569959A (en) * | 2020-12-17 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of manganese-modified carbon nanotube-loaded cobalt oxide, product and application thereof |
| CN114665108A (en) * | 2022-03-17 | 2022-06-24 | 南京师范大学 | Rare earth metal doped MOF structure oxygen electrocatalyst and preparation method thereof |
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| YUNXIA ZHUANG等: ""Co3O4/CuO hollow nanocage hybrids with high oxidase-like activity for biosensing of dopamine"", 《MATERIALS SCIENCE & ENGINEERING C》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112569927A (en) * | 2020-12-15 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of mesoporous silica-coated cobalt manganese oxide, product and application thereof |
| CN112569927B (en) * | 2020-12-15 | 2023-02-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of mesoporous silica-coated cobalt manganese oxide, product and application thereof |
| CN112569959A (en) * | 2020-12-17 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of manganese-modified carbon nanotube-loaded cobalt oxide, product and application thereof |
| CN114665108A (en) * | 2022-03-17 | 2022-06-24 | 南京师范大学 | Rare earth metal doped MOF structure oxygen electrocatalyst and preparation method thereof |
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