CN114308017A - High-activity transition metal-based integral carbon aerogel material and preparation method and application thereof - Google Patents
High-activity transition metal-based integral carbon aerogel material and preparation method and application thereof Download PDFInfo
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- CN114308017A CN114308017A CN202111462547.XA CN202111462547A CN114308017A CN 114308017 A CN114308017 A CN 114308017A CN 202111462547 A CN202111462547 A CN 202111462547A CN 114308017 A CN114308017 A CN 114308017A
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Abstract
The invention provides a high-activity transition metal-based monolithic carbon aerogel material, and a preparation method and application thereof, and belongs to the technical field of catalyst preparation. The invention evenly immerses the transition metal salt solution into the organic foam material by a simple immersion method, and calcines and synthesizes the transition metal base integral carbon aerogel material with carbon confinement in nitrogen, and the material has the advantages of high catalytic activity, high stability, easy separation and the like, can be used as a catalyst with excellent performance, and has good practical popularization and application values.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a high-activity transition metal-based monolithic carbon aerogel material, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Cobalt, manganese, iron oxides are important novel materials in the metal oxide family due to their excellent electronic structure, ionic conductivity, electron mobility and redox behavior. Co3O4Isospinel-type metal oxides have been widely studied and applied in various fields over the past several decades because they have a very large variability in composition and structure. Various transition metal catalysts catalyze the activation of Peroxymonosulfate (PMS) to SO4 ·-SO compared with OH4 ·-Has more positive reduction potential of 2.5-3.1V (vs,. OH 1.8-2.7V), wide pH application range, high oxidation selectivity and long service life (SO)4 ·-：t1/2＝30-40μs,·OH：t1/2＝10-3μ s). The activation of PMS degradation pollutants by using transition metal oxides such as cobalt, manganese, iron and the like is also one of the current hot problems. However, the transition metal oxide has the defects of easy agglomeration, serious ion leaching and the like. The preparation of supported catalysts by supporting transition metals on suitable functional supports is an effective approach to solve these problems. The graphene, the carbon nano tube, the activated carbon fiber and other emerging carbonaceous materials have rich specific surface area, surface functional groups and outstanding electrical and mechanical properties, and are widely used as catalyst carriers. However, these catalysts are usually in the form of powders, and their recycling is a troublesome problem in practical use, and may cause secondary pollution. The monolithic catalyst can solve the problem of subsequent separation of the catalyst.
Although the graphene aerogel or foam metal shows higher activity and separable characteristics in the reaction of degrading organic matters by activating PMS, the inventor finds that the graphene aerogel or the foam metal has higher price, and meanwhile, the graphene aerogel has poorer mechanical properties, is easy to break to cause the loss of active components and generate secondary pollution; the specific surface area of the foamed nickel is small, the provided active site is limited, the acting force with the active component is relatively weak, and the loss of transition metal ions is inevitable in the use process of the catalyst, so that the activity of the catalyst is reduced and secondary pollution is caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-activity transition metal-based monolithic carbon aerogel material and a preparation method and application thereof.
Specifically, the invention relates to the following technical scheme:
in a first aspect of the present invention, there is provided a high activity transition metal-based monolithic carbon aerogel material, which is a monolithic bulk material having a continuous three-dimensional network structure with a transition metal oxide uniformly dispersed thereon, wherein the transition metal oxide is cobalt oxide and/or manganese oxide.
In a second aspect of the present invention, there is provided a method for preparing the above carbon aerogel material, wherein the method comprises immersing a transition metal salt solution in an organic foam material by an immersion method, and calcining the organic foam material in nitrogen.
In a third aspect of the present invention, there is provided the use of the above-described carbon aerogel material as a monolithic catalyst.
In a fourth aspect of the invention, there is provided a monolithic catalyst comprising the above-described carbon aerogel material. Experiments prove that the monolithic catalyst prepared by the invention shows ultrahigh activity in experiments of degrading 2, 4-dichlorophenol and methyl orange by activated Peroxymonosulfate (PMS), and meanwhile, the monolithic catalyst has the characteristic of easy separation and shows higher stability in the process of multiple cyclic experiments.
In a fifth aspect of the present invention, there is provided a method for degrading 2, 4-dichlorophenol and/or methyl orange in water, the method comprising activating the 2, 4-dichlorophenol and/or methyl orange in PMS degraded water by using the above carbon aerogel material as a monolithic catalyst.
The beneficial technical effects of one or more technical schemes are as follows:
the preparation method of the carbon aerogel material provided by the technical scheme has the advantages of simple operation, high repeatability, low cost, environmental friendliness and the like; meanwhile, in the carbon aerogel material prepared by the method, the cobalt and the manganese are dispersed on the carbon foam, so that the agglomeration of the catalyst is reduced, and the catalytic performance of the catalyst is improved. Experiments prove that the carbon aerogel material prepared by the method has extremely high activity in the reaction of degrading dichlorophenol and methyl orange as an integral catalyst and has the characteristic of easy separation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a graph of catalyst degradation rates for CMF, MMF, CPF, MPF in examples of the invention.
FIG. 2 is a graph showing the degradation rates of CMF, CMF-100 deg.C, CMF-200 deg.C, CMF-1h, CMF-12h catalysts in examples and experiments of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The present invention is further described with reference to specific examples, which are provided for the purpose of illustration only and are not intended to be limiting. If the experimental conditions not specified in the examples are specified, they are generally according to the conventional conditions, or according to the conditions recommended by the sales companies; materials, reagents and the like used in examples were commercially available unless otherwise specified.
In an exemplary embodiment of the present invention, a highly reactive transition metal based monolithic carbon aerogel material is provided, wherein the carbon aerogel material is a monolithic bulk material having a continuous three-dimensional network structure with a transition metal oxide uniformly dispersed thereon, and the transition metal oxide is cobalt oxide and/or manganese oxide.
In another embodiment of the present invention, a method for preparing the above carbon aerogel material is provided, wherein the method comprises immersing a transition metal salt solution in an organic foam material by an immersion method, and calcining the organic foam material in nitrogen.
Wherein the transition metal salt is soluble salt, including cobalt salt and/or manganese salt.
The organic foam material may be a melamine carbon foam or a polyurethane foam. The organic foam used in the invention has the advantages of low cost, easy cutting, large specific surface area and the like, and is very suitable to be used as a load material of metal ions.
In another embodiment of the present invention, the preparation method comprises:
dispersing cobalt salt and/or manganese salt into an ethanol solution, and uniformly stirring to obtain a metal salt solution;
immersing the pretreated organic foam material into the metal salt solution for ultrasonic treatment and aging treatment;
and drying the organic foam material after the treatment, and calcining in a nitrogen atmosphere to obtain the organic foam material.
In yet another embodiment of the present invention, the cobalt salt is cobalt nitrate, cobalt chloride or cobalt sulfate, preferably cobalt nitrate.
The manganese salt is manganese nitrate, manganese chloride or manganese sulfate, and preferably manganese nitrate.
The concentration of the metal salt is 0.0025-0.25 mol/L.
The pretreatment method of the organic foam material comprises the following specific steps: soaking the organic foam material in ethanol, washing with deionized water, drying, and cutting into regular patterns; e.g., cut into 1cm by 1 cm.
Soaking the organic foam material in ethanol and washing the organic foam material for 2-3 times by using deionized water so as to remove impurities on the surface of the organic foam material.
The cutting into regular patterns is beneficial to the fact that the metal salt solution can be more uniformly immersed into the foam material in the subsequent immersion process.
In another embodiment of the present invention, the specific conditions of the ultrasonic and aging treatment are as follows:
ultrasonic treatment is carried out for 20-40min (preferably 30min), and aging treatment is carried out for 22-26 h (preferably 24 h); by controlling the aging treatment time, the catalytic activity of the finally prepared carbon aerogel material can be effectively improved.
In another embodiment of the present invention, the calcination is carried out under the following conditions: heating to 340-360 ℃ at a speed of 1-3 ℃/min and calcining for 3-5 h.
The metal salts and ethanol are all prepared by using analytical pure reagents, and further purification treatment is not needed.
In yet another embodiment of the present invention, the calcination is carried out at a temperature of 2 ℃/min up to 350 ℃ for 4 hours. The calcination process described above may be carried out in a tube furnace. The decomposition of metal salt is realized by controlling the heating rate, the calcining temperature and the calcining time, so that the integral catalyst material with good catalytic performance is finally obtained.
In yet another embodiment of the present invention, there is provided the use of the above-described carbon aerogel material as a monolithic catalyst.
In yet another embodiment of the present invention, there is provided a monolithic catalyst comprising the above-described carbon aerogel material. Experiments prove that the monolithic catalyst prepared by the invention shows ultrahigh activity in experiments of degrading 2, 4-dichlorophenol and methyl orange by activated Peroxymonosulfate (PMS), and meanwhile, the monolithic catalyst has the characteristic of easy separation and shows higher stability in the process of multiple cyclic experiments.
In yet another embodiment of the present invention, there is provided a method for degrading 2, 4-dichlorophenol and/or methyl orange in water, the method comprising activating 2, 4-dichlorophenol and/or methyl orange in PMS degraded water using the above-mentioned carbon aerogel material as a monolithic catalyst.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
A certain amount of cobalt nitrate (0.5mmol) was added to 40mL of absolute ethanol and stirred continuously, the melamine foam was soaked with ethanol and washed 3 times with deionized water. The treated melamine foam was cut into 1cm by 1cm volume, soaked in a nitrate solution, sonicated for half an hour and aged for 24 hours. And taking out the melamine foam soaked in the cobalt nitrate solution, and then drying in an oven. The sample obtained is placed in a tube furnace at N2Heating to 350 ℃ at the speed of 2 ℃/min in the atmosphere and calcining for 4 h. The resulting catalyst was a monolithic bulk catalyst. (named CMF)
Example 2
A certain amount of manganese nitrate (0.5mmol) was added to 40mL of absolute ethanol and stirred continuously, and the melamine foam was soaked in ethanol and washed 3 times with deionized water. The treated melamine foam was cut into 1cm by 1cm volume, soaked in a nitrate solution, sonicated for half an hour and aged for 24 hours. To be soaked in manganese nitrate solutionThe melamine foam is fished out and then placed in an oven for drying for a period of time. The sample obtained is placed in a tube furnace at N2Heating to 350 ℃ at the speed of 2 ℃/min in the atmosphere and calcining for 4 h. The resulting catalyst was a monolithic bulk catalyst.
(named MMF)
Example 3
Adding a certain amount of cobalt nitrate (0.5mmol) into 40mL of absolute ethyl alcohol, continuously stirring uniformly, soaking the polyurethane foam in the ethyl alcohol, and washing the polyurethane foam for 3 times by using deionized water. The treated polyurethane foam was cut into 1cm by 1cm volume, soaked in nitrate solution for half an hour with ultrasound and aged for 24 h. And fishing out the polyurethane foam soaked with the cobalt nitrate solution, and then drying the polyurethane foam in an oven for a period of time. The sample obtained is placed in a tube furnace at N2Heating to 350 ℃ at the speed of 2 ℃/min in the atmosphere and calcining for 4 h. The resulting catalyst was a monolithic bulk catalyst. (named CPF)
Example 4
A certain amount of manganese nitrate (0.5mmol) is added into 40mL of absolute ethyl alcohol and is continuously stirred uniformly, and polyurethane foam is soaked in the ethyl alcohol and washed 3 times by deionized water. The treated polyurethane foam was cut into 1cm by 1cm volume, soaked in nitrate solution for half an hour with ultrasound and aged for 24 h. And taking out the polyurethane foam soaked in the manganese nitrate solution, and then drying the polyurethane foam in an oven for a period of time. The sample obtained is placed in a tube furnace at N2Heating to 350 ℃ at the speed of 2 ℃/min in the atmosphere and calcining for 4 h. The resulting catalyst was a monolithic bulk catalyst. (named MPF)
FIG. 1 is a graph of catalyst degradation rates for CMF, MMF, CPF, MPF in examples 1-4 of the present invention; as can be seen, the CMF catalytic degradation efficiency is optimal, namely the cobalt-based monolithic catalyst can catalyze and degrade 95% of dichlorophenol within 5min, which provides a new idea for the monolithic catalyst to treat wastewater polluted by organic pollutants.
FIG. 2 is a graph showing the degradation rates of CMF, CMF-100 deg.C, CMF-200 deg.C, CMF-1h and CMF-12h in the examples and experimental examples of the present invention, and it can be seen that changing the calcination temperature or aging time during the preparation process has a significant effect on the catalytic degradation activity of the finally prepared monolithic catalyst.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A high-activity transition metal-based monolithic carbon aerogel material is characterized in that the carbon aerogel material is a monolithic block material and has a continuous three-dimensional network structure, transition metal oxides are uniformly dispersed on the monolithic block material, and the transition metal oxides are cobalt oxide and/or manganese oxide.
2. The method of preparing the carbon aerogel material of claim 1, comprising immersing a solution of a transition metal salt in an organic foam by an impregnation method and calcining the solution in nitrogen;
the transition metal salt is soluble salt, including cobalt salt and/or manganese salt;
the organic foam material is melamine carbon foam or polyurethane foam.
3. The method of claim 2, comprising:
dispersing cobalt salt and/or manganese salt into an ethanol solution, and uniformly stirring to obtain a metal salt solution;
immersing the pretreated organic foam material into the metal salt solution for ultrasonic treatment and aging treatment;
and drying the organic foam material after the treatment, and calcining in a nitrogen atmosphere to obtain the organic foam material.
4. The method according to claim 3, wherein the cobalt salt is cobalt nitrate, cobalt chloride or cobalt sulfate, preferably cobalt nitrate;
the manganese salt is manganese nitrate, manganese chloride or manganese sulfate, preferably manganese nitrate;
the concentration of the metal salt is 0.0025-0.25 mol/L.
5. The method according to claim 3, wherein the organic foam is pretreated by a method comprising: the organic foam material is soaked in ethanol and washed by deionized water, and then is cut into regular patterns after being dried.
6. The method of claim 3, wherein the specific conditions of the sonication and aging treatment are as follows:
ultrasonic treatment is carried out for 20-40min (preferably 30min), and aging treatment is carried out for 22-26 h (preferably 24 h).
7. The method according to claim 3, wherein the calcination is carried out under the following conditions: heating to 340-360 ℃ at 1-3 ℃/min (preferably 2 ℃/min) and calcining for 3-5 h (preferably 4 h).
8. Use of the carbon aerogel material of claim 1 and/or the carbon aerogel material obtained by the method of any of claims 2-7 as a monolithic catalyst.
9. A monolithic catalyst, characterized in that said monolithic catalyst comprises the above-mentioned carbon aerogel material.
10. A method for degrading 2, 4-dichlorophenol and/or methyl orange in water, which comprises activating 2, 4-dichlorophenol and/or methyl orange in PMS degraded water by using the carbon aerogel material of claim 1 and/or the carbon aerogel material obtained by the preparation method of any one of claims 2 to 7 as a monolithic catalyst.
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| CN115172073A (en) * | 2022-07-08 | 2022-10-11 | 同济大学 | 3D printed oxide/carbon composite aerogel electrode and preparation method thereof |
| CN116809106A (en) * | 2023-06-25 | 2023-09-29 | 重庆工商大学 | Microwave-assisted oxygen-enriched vacancy Co@NC for efficiently degrading organic pollutants X A aerogel catalyst |
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