CN109761216A - A kind of general, method that porous carbon materials are prepared based on organic zinc salt - Google Patents
A kind of general, method that porous carbon materials are prepared based on organic zinc salt Download PDFInfo
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- CN109761216A CN109761216A CN201910219676.2A CN201910219676A CN109761216A CN 109761216 A CN109761216 A CN 109761216A CN 201910219676 A CN201910219676 A CN 201910219676A CN 109761216 A CN109761216 A CN 109761216A
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Abstract
The invention belongs to technical field of material, are related to the method that one kind is general, porous carbon materials are prepared based on organic zinc salt, and porous carbon materials can be obtained using commercialized organic zinc salt as predecessor, by one-step calcination in the present invention.Gained sample has high specific surface area, porosity, electric conductivity and chemical stability and physical stability.As adsorbent material, there is good CO2Absorption and separating property；As electrode material for super capacitor, there is very high capacitor.In addition the preparation method of porous carbon materials is simple in the present invention, and required predecessor is the commercialized organic salt cheap and easy to get containing zinc, and low in raw material price, from a wealth of sources, preparation is simple, process is reproducible, it can be achieved that magnanimity preparation, is easy to amplify production.
Description
Technical field
The invention belongs to field of new materials, be related to it is a kind of it is general, extensive, inexpensively prepared based on organic zinc salt it is porous
The method of carbon material prepares porous carbon materials using organic zinc salt as raw material.
Background technique
Porous carbon materials have cellular structure abundant and higher specific surface area, high conductivity, excellent physical chemistry
The features such as stability has a wide range of applications in daily life and industrial production, such as: pernicious gas absorbs, pollutant
Absorption, the storage of gas and separation, electrode material for super capacitor etc..Meanwhile from recent years the study found that porous carbon materials
It also shows excellent catalytic activity, especially contains heteroatomic porous carbon materials, in oxygen reduction reaction, oxygen evolution reaction
Also show that very high catalytic activity.Therefore, extensive, the cheap method for preparing porous carbon materials of development is particularly significant.
Porous carbon materials mainly active charcoal (AC), activated carbon fibre (ACF), carbon molecular sieve (CMS) carbon nanotube
(CNTs), graphene etc..According to pore size, porous carbon materials can be divided into microporous carbon and meso-porous carbon material.It is wherein unordered
There are many synthetic methods, including metal catalytic to activate for mesoporous porous carbon material, and the carbonization of organic aerogel uses silicon nano
Templated synthesis etc.；Orderly porous carbon materials be obtained using molecular sieve as template, such as: have can modulation hole
The order mesoporous porous carbon materials of road structure mainly pass through mesoporous silicon material MCM-48, HMS, SBA-15, MCF, MSU-X as mould
Plate agent synthesizes to obtain；The carbon source of flexible structure can be by being converted to by the ordered mesoporous carbon material with graphite-structure under high temperature
Graphite material with higher order structures；The silicon that orderly lamellar structure porous carbon materials can also be synthesized by rational design
Material obtains for template.But above method preparation process is cumbersome, long preparation period, and template cannot reuse, cost compared with
It is high.Micro-pore carbon material mainly passes through what activation process synthesized.Activation is the widely used method for preparing porous carbon, is made
Also very extensively, such as most of biological materials can obtain high-specific surface area by the method for activation in carbon matrix precursor source
Porous carbon materials.Activation is divided into physically activated and chemical activation, and the physically activated activator that is often used has CO2, vapor etc., change
Learning activation mostly uses KOH as activator.Compared with physically activated, the porous carbon that chemical activation obtains usually has higher ratio
Surface area and porosity abundant, especially microcellular structure are abundant.But due under high temperature KOH to equipment have strong corrosion,
And it also requires further pickling is except the K, K generated in deactivation process2CO3Equal substances are answered based on porous carbon materials are wide
With prospect, it is necessary to develop more new, more simple, methods suitable for large scale preparation porous carbon materials.
Summary of the invention
The present invention provides a kind of pervasive general, and the new method of cheap large scale preparation porous carbon materials utilizes commercialization
Organic zinc salt as predecessor, porous carbon materials can be obtained by one-step calcination.Obtained material has the ratio of superelevation
Surface area, can be used as adsorbent and electrode material for super capacitor, and elctro-catalyst etc. uses.This method preparation process is easy, former
Expect cheap, from a wealth of sources, it can be achieved that magnanimity preparation, is easy to amplify production.
To achieve the above object, technical solution provided by the invention are as follows:
A kind of general, method that porous carbon materials are prepared based on organic zinc salt, comprising the following steps:
Using the organic zinc salt for containing more carbon as carbon matrix precursor, uniformly it is placed in quartz boat (it is required that sample is uniform
Be layered on quartz boat bottom, to guarantee that sample is heated evenly and can be completed in a relatively short time carbonization and Zn element is waved
Hair process)；It will be placed in tube furnace in quartz boat again, under nitrogen stream holding, from the slow temperature programming of room temperature to required carbon
Change temperature T, and be carbonized 0.5-5 hours at carburizing temperature T, the carburizing temperature T is 500-1000 DEG C: when carburizing temperature T exists
At 900-1000 DEG C, directly it is cooled to room temperature to obtain porous carbon materials after carbonization；When carburizing temperature T is at 500-900 DEG C, carbonization
After be cooled to room temperature after, it is also necessary to remove remaining element Zn through overpickling and obtain porous carbon materials.Obtained porous carbon materials
BET specific surface area be 1000-4000m2/g；Aperture is configured to based on micropore, has ultramicropore abundant (< 0.7nm), contains
Have mesoporous, pore diameter range is in 0.3-30nm, and wherein carbon element content is 80% or more, according to using the difference of predecessor may also
Contain the hetero atoms such as N, S, P, B.
The organic zinc salt includes glycine zinc salt (C4H8N2O4Zn), zinc citrate (C12H10O14Zn3), zinc acrylate resin
(C6H6O4Zn), zinc dimethacrylate (C8H10O4Zn), zinc acetylacetonate (C10H14O4Zn), zinc gluconate (C12H22O4Zn)、
8-hydroxyquinoline zinc salt (C18H12N2O2Zn), ethylenediamine tetraacetic acid disodium zinc salt salt (C10H12N2Na2O8Zn) p-methyl benzenesulfonic acid zinc
(CH3C6H4SO3)2Zn), zinc lactate (C6H10O6Zn), in addition, organic zinc salt can contain a small amount of crystallization water.
The carbonization time is different, and the porosity of gained porous carbon is different, and carbonization time is preferably 2-4 hours.According to
The difference of required application field can easily control the pore structure of material by adjusting carburizing temperature and time.
The nitrogen stream flow rates demand can guarantee that continuous purging, flow velocity are 50-100 milliliters per minute.
The temperature programming speed is 1-10 degrees celsius/minute, preferably 5 degrees celsius/minutes.In Temperature Programmed Processes
In, heating rate is unsuitable too fast, is easy to cause uneven heating even because heating is too fast, and then cause carbonization uneven, heating rate
For 5 degrees celsius/minutes, can guarantee to save the time while being heated evenly.
Further, before the slow temperature programming of room temperature, the sky in tube furnace first is drained with nitrogen purging a period of time
Gas, or first by tubular type stove evacuation, three times with nitrogen displacement, it is ensured that high pure nitrogen atmosphere has avoided oxygen or other gases from depositing
Other reactions such as oxidation can occur in making carbonisation.
The invention has the benefit that required precursor sources are extensive, cheap, preparation method is simple, it is only necessary to a step
Calcining, while gained porous carbon materials have the specific surface area of superelevation, ultra-microporous abundant and more chemical imperfection, tool
There is high gas absorption performance, while as electrode material for super capacitor, there is very high capacitance out, as electro-catalysis
Agent has high catalytic activity.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of gained sample in embodiment 1.
Fig. 2 is the transmission electron microscope figure of gained sample in embodiment 1.
Fig. 3 is the nitrogen adsorption curve graph of 1 gained sample of embodiment.
Fig. 4 is the CO of 1 gained sample of embodiment2Adsorption curve figure.
Fig. 5 is the cyclic voltammetry curve figure of 1 gained sample of embodiment.
Specific embodiment
The present invention is described in further detail below by embodiment, but scope of the presently claimed invention is not by this
The limitation of a little embodiments.Meanwhile embodiment has been merely given as reaching the partial condition of this purpose, is not meant to must satisfy this
This purpose just may be implemented in a little conditions.
Embodiment 1:
Porous carbon materials are prepared according to the following steps:
Step 1: with zinc citrate (C12H10O14Zn3) it is used as carbon matrix precursor.
Step 2: 1.00 grams of zinc citrates are weighed and are uniformly placed on 1*3cm2Quartz boat bottom, to guarantee that sample is heated
Uniformly and carbonization and Zn element evaporation process can be completed in a relatively short time, from the slow temperature programming of room temperature to 1000
℃；
Step 3: in the case where keeping nitrogen stream, by zinc salt material temperature control at 1000 DEG C, activation time is 2 hours.
Step 4: it under nitrogen flowing, is cooled to room temperature, directly obtains porous carbon materials.
Temperature programming speed described in step 2 is 5 degrees celsius/minutes.Nitrogen stream flow velocity described in step 3 is 50
Milliliter is per minute.
The not stringent limitation of heating equipment of the present invention to carbonisation, such as heating furnace commonly used in the prior art is i.e.
Can, preferred tube furnace is more convenient because the temperature control of tube furnace can be completed by the thermocouple of its own configuration.
Fig. 1 is the scanning electron microscope diagram of sample obtained by this embodiment, it can be seen that sample is loose and porous structure.
Fig. 2 is the transmission electron microscopy figure of sample, and display sample is mainly undefined structure.Fig. 3 is carbon material obtained by this embodiment
Nitrogen adsorption curve, using BET method calculate sample specific surface area be 2722cm3g-1, adsorption curve is significant in low-pressure area
Rise, while hysteresis loop occur in the higher section of opposite pressure, shows that sample is containing micropore and mesoporous grade Porous materials.
Fig. 4 be this embodiment sample CO2Adsorption curve, at one atm CO2Adsorbance is 88cm3g-1.Fig. 5 is this
Embodiment sample cyclic voltammetry curve, in 10mV s-1Sweep under speed, the capacitor of sample is 205F g-1。
Embodiment 2:
Step 1: using zinc gluconate as carbon matrix precursor.
Step 2: 1.00 grams of zinc gluconates are weighed and are uniformly placed on 1*3cm2Quartz boat bottom, thus guarantee sample by
It is hot uniformly and to be completed in a relatively short time carbonization and Zn element evaporation process, from the slow temperature programming of room temperature to 1000
℃；
Step 3: in the case where keeping nitrogen stream, by zinc salt material temperature control at 1000 DEG C, activation time is 3 hours.
Step 4: it under nitrogen flowing, is cooled to room temperature, directly obtains porous carbon materials.
Temperature programming speed described in step 2 is 2 degrees celsius/minutes.Nitrogen stream flow velocity described in step 3 is
100 milliliters per minute.
Embodiment 3:
Step 1: using glycine zine as carbon matrix precursor.
Step 2: 1.00 grams of glycine zines are weighed and are uniformly placed on 1*3cm2Quartz boat bottom, to guarantee that sample is heated
Uniformly and carbonization and Zn element evaporation process can be completed in a relatively short time, from the slow temperature programming of room temperature to 1000
℃；
Step 3: in the case where keeping nitrogen stream, by zinc salt material temperature control at 1000 DEG C, activation time is 2 hours.
Step 4: it under nitrogen flowing, is cooled to room temperature, directly obtains porous carbon materials.
Temperature programming speed described in step 2 is 10 degrees celsius/minutes.Nitrogen stream flow velocity described in step 3 is
80 milliliters per minute.
Embodiment 4:
Step 1: with zinc lactate (C6H10O6Zn) it is used as carbon matrix precursor.
Step 2: 1.00 grams of zinc lactates are weighed and are uniformly placed on 1*3cm2Quartz boat bottom, to guarantee that sample is heated equal
It is even and carbonization and Zn element evaporation process can be completed in a relatively short time, from the slow temperature programming of room temperature to 900 DEG C；
Step 3: in the case where keeping nitrogen stream, by zinc salt material temperature control at 900 DEG C, activation time is 3 hours.
Step 4: it under nitrogen flowing, is cooled to room temperature, directly obtains porous carbon materials.
Temperature programming speed described in step 2 is 5 degrees celsius/minutes.Nitrogen stream flow velocity described in step 3 is 50
Milliliter is per minute.
Embodiment 5:
Step 1: with zinc acetylacetonate (C10H14O4Zn) it is used as carbon matrix precursor.
Step 2: 1.00 grams of zinc acetylacetonates are weighed and are uniformly placed on 1*3cm2Quartz boat bottom, thus guarantee sample by
It is hot uniformly and to be completed in a relatively short time carbonization and Zn element evaporation process, from the slow temperature programming of room temperature to 500
℃；
Step 3: in the case where keeping nitrogen stream, by zinc salt material temperature control at 500 DEG C, activation time is 4 hours.
Step 4: under nitrogen flowing, being cooled to room temperature, and product acid is removed and removes remaining element Zn, obtains porous carbon
Material.
Temperature programming speed described in step 2 is 8 degrees celsius/minutes.Nitrogen stream flow velocity described in step 3 is 60
Milliliter is per minute.
The above, only presently preferred embodiments of the present invention for those of ordinary skill in the art can bases
Technical solution of the present invention and technical concept make other various corresponding changes and modifications, and all these change and modification are all
It should belong to the protection scope of the claims in the present invention.
Claims (7)
- The method that 1. one kind is general, prepares porous carbon materials based on organic zinc salt, which is characterized in that this method includes following step It is rapid:Using organic zinc salt as carbon matrix precursor, it is uniformly laid in quartz boat bottom, then will be placed in tube furnace in quartz boat, Under nitrogen stream is kept, from the slow temperature programming of room temperature to required carburizing temperature T, and it is carbonized 0.5-5 hours at carburizing temperature T, The carburizing temperature T is 500-1000 DEG C: when carburizing temperature T is at 900-1000 DEG C, being directly cooled to room temperature to obtain after carbonization Porous carbon materials；When carburizing temperature T is at 500-900 DEG C, after carbonization is cooled to room temperature, also need to remove remaining member through overpickling Plain Zn obtains porous carbon materials；The BET specific surface area of the porous carbon materials is 1000-4000m2/g；Aperture is configured to based on micropore, has abundant Ultramicropore < 0.7nm, containing mesoporous, pore diameter range is in 0.3-30nm；Carbon element content is 80% or more, according to using predecessor Difference may contain other hetero atoms.
- 2. the method that one kind according to claim 1 is general, prepares porous carbon materials based on organic zinc salt, feature exist In the organic zinc salt includes glycine zinc salt (C4H8N2O4Zn), zinc citrate (C12H10O14Zn3), zinc acrylate resin (C6H6O4Zn), zinc dimethacrylate (C8H10O4Zn), zinc acetylacetonate (C10H14O4Zn), zinc gluconate (C12H22O4Zn)、 8-hydroxyquinoline zinc salt (C18H12N2O2Zn), ethylenediamine tetraacetic acid disodium zinc salt salt (C10H12N2Na2O8Zn) p-methyl benzenesulfonic acid zinc (CH3C6H4SO3)2Zn), zinc lactate (C6H10O6Zn), in addition, organic zinc salt can contain a small amount of crystallization water.
- 3. the method that one kind according to claim 1 is general, prepares porous carbon materials based on organic zinc salt, feature exist In the carbonization time is preferably 2-4 hours.
- 4. the method that one kind according to claim 1 is general, prepares porous carbon materials based on organic zinc salt, feature exist In the nitrogen stream flow velocity is 50-100 milliliters per minute.
- 5. the method that one kind according to claim 1 is general, prepares porous carbon materials based on organic zinc salt, feature exist In the temperature programming speed is 1-10 degrees celsius/minute.
- 6. the method that one kind according to claim 5 is general, prepares porous carbon materials based on organic zinc salt, feature exist In the temperature programming speed is preferably 5 degrees celsius/minutes.
- 7. the method that one kind according to claim 1 is general, prepares porous carbon materials based on organic zinc salt, feature exist In before the slow temperature programming of room temperature, first with nitrogen sparge tube formula furnace to drain air, or first by tubular type stove evacuation, nitrogen Gas displacement, it is ensured that high pure nitrogen atmosphere.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110182781A (en) * | 2019-05-24 | 2019-08-30 | 宿州学院 | A kind of preparation method of supercapacitor three-dimensional framework charcoal nanometer sheet |
| CN110255557A (en) * | 2019-07-03 | 2019-09-20 | 厦门理工学院 | A kind of high porosity porous charcoal and its preparation method and application |
| CN111994897A (en) * | 2020-09-08 | 2020-11-27 | 许昌学院 | Simple preparation method of honeycomb porous carbon with high specific surface area |
| CN113659136A (en) * | 2021-07-29 | 2021-11-16 | 武汉理工大学 | Organic acid radical inorganic salt pyrolytic carbon electrode material and preparation method and application thereof |
| CN113782710A (en) * | 2021-09-17 | 2021-12-10 | 中国计量大学 | High-performance chargeable and dischargeable aqueous zinc-iodine battery and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108584944A (en) * | 2018-06-26 | 2018-09-28 | 北京化工大学 | A kind of preparation method of the ultracapacitor rich nitrogen grading porous carbon electrode material of high-specific surface area |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108584944A (en) * | 2018-06-26 | 2018-09-28 | 北京化工大学 | A kind of preparation method of the ultracapacitor rich nitrogen grading porous carbon electrode material of high-specific surface area |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110182781A (en) * | 2019-05-24 | 2019-08-30 | 宿州学院 | A kind of preparation method of supercapacitor three-dimensional framework charcoal nanometer sheet |
| CN110255557A (en) * | 2019-07-03 | 2019-09-20 | 厦门理工学院 | A kind of high porosity porous charcoal and its preparation method and application |
| CN111994897A (en) * | 2020-09-08 | 2020-11-27 | 许昌学院 | Simple preparation method of honeycomb porous carbon with high specific surface area |
| CN111994897B (en) * | 2020-09-08 | 2023-05-02 | 许昌学院 | Simple preparation method of honeycomb porous carbon with high specific surface area |
| CN113659136A (en) * | 2021-07-29 | 2021-11-16 | 武汉理工大学 | Organic acid radical inorganic salt pyrolytic carbon electrode material and preparation method and application thereof |
| CN113659136B (en) * | 2021-07-29 | 2023-02-07 | 武汉理工大学 | Organic acid radical inorganic salt pyrolytic carbon electrode material and preparation method and application thereof |
| CN113782710A (en) * | 2021-09-17 | 2021-12-10 | 中国计量大学 | High-performance chargeable and dischargeable aqueous zinc-iodine battery and preparation method thereof |
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Application publication date: 20190517 |