CN109420491A - A kind of preparation method of carbon nanotube-manganese dioxide composite catalyst - Google Patents
A kind of preparation method of carbon nanotube-manganese dioxide composite catalyst Download PDFInfo
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- CN109420491A CN109420491A CN201710730515.0A CN201710730515A CN109420491A CN 109420491 A CN109420491 A CN 109420491A CN 201710730515 A CN201710730515 A CN 201710730515A CN 109420491 A CN109420491 A CN 109420491A
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- carbon nanotube
- manganese dioxide
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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Abstract
The invention discloses a kind of carbon nanotube-manganese dioxide composite catalyst preparation methods, comprising: (1) carbon nanotube of carboxylation is added in deionized water, ultrasonic disperse handles 1~2h and is heated to 75~85 DEG C, obtains carbon nano tube suspension；(2) liquor potassic permanganate that concentration is 0.01~0.5mol/L is added in Xiang Shangshu carbon nano tube suspension, it stirs evenly, it is 2~6 that 1mol/L acid solution, which is added, and adjusts pH value, continue stirring 12~for 24 hours under the conditions of temperature is 100~140 DEG C of oil baths, obtains containing carbon nanotube-manganese dioxide mixed solution；(3) it filters above-mentioned containing carbon nanotube-manganese dioxide mixed solution, is washed 3~5 times with 0.1~1mol/L acid solution and deionized water respectively, dry 1~2h, obtains carbon nanotube-manganese dioxide composite catalyst in 50~60 DEG C of baking ovens.Carbon nanotube-manganese dioxide composite catalyst catalytic activity with higher and preferable stability in the present invention.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of carbon nanotube-manganese dioxide composite catalyst system
Preparation Method.
Background technique
MnO2It is the relatively broad multi-functional transition metal oxide of research, its friendly, cheap, resource with environment
The advantages that abundant, and there is excellent electrochemical performance, it has been achieved in the commercialization process as battery electrode material huge
Big success.In recent years, effect novel as brought by material nano, people are for nanometer MnO2Research increasingly
It is interested, about nanometer MnO2Electrode material report as supercapacitor is also commonplace.But nanometer MnO2As super
It is easy to reunite during capacitor electrode material, to make its cyclicity be deteriorated, it could even be possible to losing nanosizing institute
Bring excellent properties.
Carbon nanotube is due to having specific one-dimensional tubular structure, big reference area, superpower mechanical performance, high change
It learns and thermal stability becomes the hot spot studied in recent ten years.Especially carbon nanotube is in anti-SO2Poisoning aspect shows excellent
Performance.Chinese patent CN201210246086.7 is compound by equi-volume impregnating Supported Manganese, cerium using carbon nanotube as carrier
Oxide is active material, and denitrating catalyst has been made.In actual use, manganese, cerium composite oxides particle are easily assembled
To reduce performance.However, currently, active component is mainly loaded to carrier using infusion process in the technology of preparing of catalyst
On, active component particles are easy to reunite, it is difficult to guarantee that active component is evenly dispersed in carrier surface.
For this reason, it is necessary in view of the above-mentioned problems, propose a kind of preparation side of carbon nanotube-manganese dioxide composite catalyst
Method is able to solve problems of the prior art.
Summary of the invention
The purpose of the present invention is to provide a kind of carbon nanotube-manganese dioxide composite catalyst preparation methods, to overcome
Deficiency in the prior art.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of carbon nanotube-manganese dioxide composite catalyst, comprising:
(1) carbon nanotube of carboxylation being added in deionized water, ultrasonic disperse handles 1~2h and is heated to 75~85 DEG C,
Obtain carbon nano tube suspension；
(2) liquor potassic permanganate that concentration is 0.01~0.5mol/L, stirring are added in Xiang Shangshu carbon nano tube suspension
Uniformly, be added 1mol/L acid solution adjust pH value be 2~6, temperature be 100~140 DEG C of oil baths under the conditions of continue stirring 12~
For 24 hours, it obtains containing carbon nanotube-manganese dioxide mixed solution；
(3) it is filtered above-mentioned containing carbon nanotube-manganese dioxide mixed solution, respectively with 0.1~1mol/L acid solution
It is washed 3~5 times with deionized water, dry 1~2h, obtains carbon nanotube-manganese dioxide composite catalyzing in 50~60 DEG C of baking ovens
Agent.
Preferably, in step (1), the preparation method of the carbon nanotube of the carboxylation includes:
1) carbon nanotube is added in the mixed acid containing concentrated nitric acid and the concentrated sulfuric acid, is stood after 20~30min of ultrasound, water-bath adds
Heat is cooling to 110~120 DEG C, 20~30min of magnetic agitation, obtains mixed solution；
2) distilled water dilution is added in mixed liquor after cooling, upper layer acid solution is removed in centrifuge separation, filters, and washs, and does
Dry, grinding obtains the carbon nanotube of carboxylation.
Preferably, in step (1), in the carbon nano tube suspension, the mass fraction of the carbon nanotube is 5~
20%.
Preferably, the acid solution is selected from one of hydrochloric acid solution, sulfuric acid solution and nitric acid solution.
Preferably, in the carbon nanotube-manganese dioxide composite catalyst, the quality of the carbon nanotube and manganese dioxide
The ratio between be 1:10~50.
Preferably, in the carbon nanotube-manganese dioxide composite catalyst, the quality of the carbon nanotube and manganese dioxide
The ratio between be 1:15~30.
Compared with the prior art, the advantages of the present invention are as follows: carbon nanotube-manganese dioxide composite catalyst in the present invention
Catalytic activity with higher and preferable stability.
Specific embodiment
The present invention is described further by the following example: according to following embodiments, the present invention may be better understood.
However, as it will be easily appreciated by one skilled in the art that specific material ratio, process conditions and its result described in embodiment are only used
In illustrating the present invention, without the present invention described in detail in claims should will not be limited.
The present invention discloses a kind of preparation method of carbon nanotube-manganese dioxide composite catalyst, comprising:
(1) carbon nanotube of carboxylation being added in deionized water, ultrasonic disperse handles 1~2h and is heated to 75~85 DEG C,
Obtain carbon nano tube suspension；
(2) liquor potassic permanganate that concentration is 0.01~0.5mol/L, stirring are added in Xiang Shangshu carbon nano tube suspension
Uniformly, be added 1mol/L acid solution adjust pH value be 2~6, temperature be 100~140 DEG C of oil baths under the conditions of continue stirring 12~
For 24 hours, it obtains containing carbon nanotube-manganese dioxide mixed solution；
(3) it is filtered above-mentioned containing carbon nanotube-manganese dioxide mixed solution, respectively with 0.1~1mol/L acid solution
It is washed 3~5 times with deionized water, dry 1~2h, obtains carbon nanotube-manganese dioxide composite catalyzing in 50~60 DEG C of baking ovens
Agent.
In above-mentioned steps (1), in the carbon nano tube suspension, the mass fraction of the carbon nanotube is 5~20%, excellent
Choosing, the mass fraction of the carbon nanotube is 5~15%, it is furthermore preferred that the mass fraction of the carbon nanotube is 10%.
In above steps, the acid solution is selected from one of hydrochloric acid solution, sulfuric acid solution and nitric acid solution, preferably
, the acid solution is selected from hydrochloric acid solution.
In the carbon nanotube according to made from the above method-manganese dioxide composite catalyst, the carbon nanotube and titanium dioxide
The mass ratio of manganese is 1:10~50, it is preferred that the carbon nanotube and the mass ratio of manganese dioxide are 1:15~30, more excellent
Choosing, the mass ratio of the carbon nanotube and manganese dioxide is 1:20.
In one embodiment, the preparation method of the carbon nanotube of the carboxylation includes:
1) carbon nanotube is added in the mixed acid containing concentrated nitric acid and the concentrated sulfuric acid, is stood after 20~30min of ultrasound, water-bath adds
Heat is cooling to 110~120 DEG C, 20~30min of magnetic agitation, obtains mixed solution；
2) distilled water dilution is added in mixed liquor after cooling, upper layer acid solution is removed in centrifuge separation, filters, and washs, and does
Dry, grinding obtains the carbon nanotube of carboxylation.
Embodiment
1, the carbon nanotube of carboxylation is prepared
1) 100mL is added containing concentrated nitric acid and concentrated sulfuric acid volume than in the mixed acid for 1:3 in 5g carbon nanotube, it is ultrasonic
It is stood after 30min, heating water bath is cooling to 115 DEG C, magnetic agitation 25min, obtains mixed solution；
2) distilled water dilution is added in mixed liquor after cooling, upper layer acid solution is removed in centrifuge separation, filters, and washs, and does
Dry, grinding obtains the carbon nanotube of carboxylation.
2, carbon nanotube-manganese dioxide composite catalyst is prepared
(1) carbon nanotube of carboxylation is added in deionized water, ultrasonic disperse handles 1~2h and is heated to 80 DEG C, obtains
The suspension that carbon nanotube mass score is 10%；
(2) liquor potassic permanganate that concentration is 0.25mol/L is added in Xiang Shangshu carbon nano tube suspension, stirs evenly,
It is 4 that 1mol/L hydrochloric acid solution, which is added, and adjusts pH value, continues to stir 18h under the conditions of temperature is 120 DEG C of oil baths, obtains receiving containing carbon
Mitron-manganese dioxide mixed solution；
(3) filtered above-mentioned containing carbon nanotube-manganese dioxide mixed solution, respectively with 0.5mol/L hydrochloric acid solution and
Deionized water is washed 3~5 times, and dry 2h, obtains carbon nanotube-manganese dioxide composite catalyst in 60 DEG C of baking ovens.
In the carbon nanotube according to made from the method in above-described embodiment-manganese dioxide composite catalyst, carbon nanotube and
The mass ratio of manganese dioxide is 1:20.
It is compound by carrying out manganese dioxide and carbon nanotube in the present invention, since the specific surface area of carbon nanotube is larger,
Manganese dioxide can be uniformly dispersed in its surface, and therefore, carbon nanotube-manganese dioxide composite catalyst in the present invention has
Higher catalytic activity and preferable stability.
Finally, it is to be noted that, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.
Claims (6)
1. a kind of carbon nanotube-manganese dioxide composite catalyst preparation method characterized by comprising
(1) carbon nanotube of carboxylation is added in deionized water, ultrasonic disperse handles 1~2h and is heated to 75~85 DEG C, obtains
Carbon nano tube suspension；
(2) liquor potassic permanganate that concentration is 0.01~0.5mol/L is added in Xiang Shangshu carbon nano tube suspension, stirs evenly,
It is 2~6 that 1mol/L acid solution, which is added, and adjusts pH value, continues stirring 12~for 24 hours under the conditions of temperature is 100~140 DEG C of oil baths, obtains
To containing carbon nanotube-manganese dioxide mixed solution；
(3) by it is above-mentioned containing carbon nanotube-manganese dioxide mixed solution filter, respectively with 0.1~1mol/L acid solution with go
Ion water washing 3~5 times, dry 1~2h, obtains carbon nanotube-manganese dioxide composite catalyst in 50~60 DEG C of baking ovens.
2. carbon nanotube according to claim 1-manganese dioxide composite catalyst preparation method, which is characterized in that step
Suddenly in (1), the preparation method of the carbon nanotube of the carboxylation includes:
1) carbon nanotube is added in the mixed acid containing concentrated nitric acid and the concentrated sulfuric acid, is stood after 20~30min of ultrasound, heating water bath is extremely
It is 110~120 DEG C, 20~30min of magnetic agitation, cooling, obtain mixed solution；
2) distilled water dilution being added in mixed liquor after cooling, upper layer acid solution is removed in centrifuge separation, filters, and washs, and it is dry, it grinds
Mill, obtains the carbon nanotube of carboxylation.
3. carbon nanotube according to claim 1-manganese dioxide composite catalyst preparation method, which is characterized in that step
Suddenly in (1), in the carbon nano tube suspension, the mass fraction of the carbon nanotube is 5~20%.
4. carbon nanotube according to claim 1-manganese dioxide composite catalyst preparation method, which is characterized in that institute
It states acid solution and is selected from one of hydrochloric acid solution, sulfuric acid solution and nitric acid solution.
5. carbon nanotube according to claim 1-manganese dioxide composite catalyst preparation method, which is characterized in that institute
It states in carbon nanotube-manganese dioxide composite catalyst, the mass ratio of the carbon nanotube and manganese dioxide is 1:10~50.
6. carbon nanotube according to claim 5-manganese dioxide composite catalyst preparation method, which is characterized in that institute
It states in carbon nanotube-manganese dioxide composite catalyst, the mass ratio of the carbon nanotube and manganese dioxide is 1:15~30.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110429289A (en) * | 2019-08-19 | 2019-11-08 | 北京林业大学 | A kind of preparation method of the catalyst for direct lignin alkaline fuel cell anode |
| CN113289615A (en) * | 2021-06-17 | 2021-08-24 | 佛山市诺蓝环保科技有限公司 | Preparation method and application of carbon nano tube in-situ loaded manganese dioxide catalyst |
| CN113634248A (en) * | 2020-05-11 | 2021-11-12 | 山东大学 | Carbon-doped manganese dioxide catalyst for activating peroxymonosulfate and preparation method and application thereof |
-
2017
- 2017-08-23 CN CN201710730515.0A patent/CN109420491A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110429289A (en) * | 2019-08-19 | 2019-11-08 | 北京林业大学 | A kind of preparation method of the catalyst for direct lignin alkaline fuel cell anode |
| CN113634248A (en) * | 2020-05-11 | 2021-11-12 | 山东大学 | Carbon-doped manganese dioxide catalyst for activating peroxymonosulfate and preparation method and application thereof |
| CN113634248B (en) * | 2020-05-11 | 2022-12-30 | 山东大学 | Carbon-doped manganese dioxide catalyst for activating peroxymonosulfate and preparation method and application thereof |
| CN113289615A (en) * | 2021-06-17 | 2021-08-24 | 佛山市诺蓝环保科技有限公司 | Preparation method and application of carbon nano tube in-situ loaded manganese dioxide catalyst |
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