CN108609604A - A kind of phosphorus doping micropore/meso-porous carbon material and preparation method thereof - Google Patents
A kind of phosphorus doping micropore/meso-porous carbon material and preparation method thereof Download PDFInfo
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- CN108609604A CN108609604A CN201810591723.1A CN201810591723A CN108609604A CN 108609604 A CN108609604 A CN 108609604A CN 201810591723 A CN201810591723 A CN 201810591723A CN 108609604 A CN108609604 A CN 108609604A
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Abstract
A kind of phosphorus doping micropore/meso-porous carbon material and preparation method thereof, belongs to preparation and the applied technical field of carbon material.It is to be dried after cleaning up gumbo with clear water, is lyophilized 48 hours~96 hours under the conditions of 45 DEG C~80 DEG C, obtains freeze-drying gumbo；It is heat-treated 2 hours~4 hours under the conditions of 700 DEG C~900 DEG C again, obtains phosphorus doping micropore/meso-porous carbon material.Prepared phosphorus doping micropore/meso-porous carbon material is three-dimensional porous structure, and micropore pore size is 0.5~1.8nm, and micropore pore volume is 0.3~0.8cm3/ g, mesoporous pore size are 5~10nm, and pore volume is 0.8~1.5cm3/ g, BET specific surface area are 600~900m2The doping content of/g, phosphorus atoms are 4~12wt%.Prepared phosphorus doping micropore/meso-porous carbon material has big specific surface area, big porosity and regulatable pore-size distribution, also the hole with micropore and mesoporous two kinds of sizes, these unique porous structures make phosphorus doping micropore/meso-porous carbon material have important application prospect in many fields simultaneously.
Description
Technical field
The invention belongs to the preparation of carbon material and applied technical fields, and in particular to one kind is using biomass gumbo as predecessor
Phosphorus doping micropore/meso-porous carbon material and preparation method thereof, the phosphorus doping micropore/meso-porous carbon material have big specific surface area,
Big porosity and micropore/mesoporous dual pore passage structure.
Background technology
Porous carbon materials are due to having many advantages, such as that large specific surface area, porosity are big and pore passage structure is easy to regulation and control, especially
The advantages of taking into account porous structure and the excellent physicochemical properties of carbon material, are that other materials is incomparable, in catalysis, are inhaled
The fields such as the attached, energy are widely used.In order to further improve the structure of porous carbon materials, porous carbon materials are widened
On the one hand the hetero atoms such as nitrogen, sulphur, phosphorus can be introduced into the change of the skeleton or surface regulation and control carbon material of carbon material by application field
Property is learned, on the other hand can accelerate transmission rate of the guest molecule in carbon material by constructing multiple pore passage structure.It prepares
Heteroatom doping, the porous carbon materials with multiple pore passage structure are carbon material field matters of utmost importance urgently to be resolved hurrily at present, at
For the research hotspot of scientific research field and industrial circle.
In terms of preparing porous carbon materials, using block copolymer as the mantle plate method of template and using mesoporous silicon oxide as mould
The hard template method of plate be prepare the common method of ordered mesoporous carbon material at present, but these method synthesis step complexity it is cumbersome,
Synthesis cost height, low yield, are not suitable for industrialization large-scale production.Preparing the porous carbon materials with multiple pore passage structure
Aspect generally requires the template using two or more, and synthesis condition is complicated, harsh.In Heteroatom doping side
Face, main includes doping and post-processing two methods in situ.Doping in situ refers to being introduced in situ during preparing porous carbon
Containing heteroatomic predecessor, then hetero atom is introduced into carbon skeleton by the method for Pintsch process；And post treatment method one
As be the porous carbon materials that will prepare containing the processing of heteroatomic gas high temperature, pass through the change between hetero atom and carbon skeleton
It learns reaction and realizes heteroatomic doping.Heteroatom doping has the preparation method side of the porous carbon materials of multiple pore passage structure at present
Face, still exist many problems need it is further solve, for example, building-up process very complicated, using a large amount of organic reagent,
Price is relatively expensive, and preparation process environment is unfriendly, and low output is not suitable for commercial Application.Therefore, develop be simple and efficient it is miscellaneous
The atom doped porous carbon preparation method for material with multiple pore passage structure becomes the preparation of carbon material and applied technical field is ground
One of important directions studied carefully have important application prospect in fields such as catalysis, absorption, the energy.
Invention content
The purpose of the present invention is overcoming the shortcomings of existing Heteroatom doping porous carbon preparation method for material, a kind of letter is provided
Phosphorus doping micropore/meso-porous carbon material and preparation method thereof single, efficiently, inexpensive.
A kind of preparation method of phosphorus doping micropore/meso-porous carbon material of the present invention, its step are as follows：
(1) 10g~60g gumbos are cleaned up with clear water, it is small that 24 hours~36 is dried under the conditions of 100 DEG C~120 DEG C
When, obtain dry gumbo raw material；
(2) the drying gumbo for obtaining step (1) is as (Beijing Fourth Ring freeze drier, LGJ-30H) in freeze dryer ,-
It is lyophilized 48 hours~96 hours under the conditions of 45 DEG C~-80 DEG C, obtains freeze-drying gumbo；
(3) the freeze-drying gumbo for obtaining step (2) is heat-treated 2 hours~4 hours under the conditions of 700 DEG C~900 DEG C, obtains
Phosphorus doping micropore/meso-porous carbon material.
Prepared phosphorus doping micropore/meso-porous carbon material is three-dimensional porous structure, and micropore pore size is 0.5~1.8nm, micro-
Hole pore volume is 0.3~0.8cm3/ g, mesoporous pore size are 5~10nm, and pore volume is 0.8~1.5cm3/ g, BET specific surface area
For 600~900m2The doping content of/g, phosphorus atoms are 4~12wt%.
It is an advantage of the invention that：
1) draw doped with phosphorus atoms, phosphorus atoms in the skeleton of phosphorus doping micropore/meso-porous carbon material prepared by the present invention
Enter, the fundamental propertys such as acid-base property, the catalytic activity of carbon skeleton can be regulated and controled, has expanded the application field of carbon material.
2) phosphorus doping micropore/meso-porous carbon material prepared by the present invention has big specific surface area, big porosity and can
The pore-size distribution of regulation and control, while also the hole with micropore and mesoporous two kinds of sizes, these unique porous structures make phosphorus doping
Micropore/meso-porous carbon material has important application prospect in many fields.
3) present invention in phosphorus doping micropore/meso-porous carbon material preparation method, step is simple, easy to operate, of low cost,
And it can realize phosphorus doping micropore/meso-porous carbon material porous structure and hetero atom by controlling the experiment parameters such as reaction time
The regulation and control of content.
4) present invention in phosphorus doping micropore/meso-porous carbon material preparation method, using biomass gumbo as unique forerunner
Object need not add any template, catalyst and organic reagent, greatly improve combined coefficient.
5) it in the present invention in the preparation method of phosphorus doping micropore/meso-porous carbon material, is obtained by direct high-temperature calcination gumbo
Phosphorus doping micropore/meso-porous carbon material need not introduce additional phosphorus doping reagent, have the advantages that be simple and efficient.
Description of the drawings
Fig. 1：The electron scanning micrograph of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1.
Fig. 2：The nitrogen adsorption desorption curve of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1.
Fig. 3：The mesoporous pore size distribution curve of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1.
Fig. 4：The micropore size distribution curve of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1.
Fig. 5：The P2p x-ray photoelectron spectroscopies of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1.
Specific implementation mode
Embodiment 1
(1) 10g gumbos are cleaned up with clear water, is dried 36 hours under the conditions of 100 DEG C, it is former to obtain dry gumbo
Material, product quality is 9g.
(2) the drying gumbo for obtaining step (1) is as (Beijing Fourth Ring freeze drier, LGJ-30H) in freeze dryer ,-
It is lyophilized 96 hours under the conditions of 45 DEG C, obtains freeze-drying gumbo, product quality is 8g.
(3) the freeze-drying gumbo for obtaining step (2) is heat-treated 4 hours at 700 DEG C, obtains phosphorus doping micropore/mesoporous carbon materials
Material, product quality is 6g.
Prepared phosphorus doping micropore/meso-porous carbon material is three-dimensional porous structure, and micropore pore size is 0.5nm, micropore hole
Volume is 0.3cm3/ g, mesoporous pore size are 5nm, pore volume 0.8cm3/ g, BET specific surface area 600m2/g；Phosphorus atoms
Doping content is 12wt%.
The electron scanning micrograph of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1 is as shown in Figure 1.It can be with
Find out, phosphorus doping micropore/meso-porous carbon material is made of micron bar and irregular micro particles, the carbon materials of these different-shapes
Different component parts of the material in gumbo.
The nitrogen adsorption desorption curve of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1 is shown in Fig. 2.It can be seen that sample
Product show apparent hysteresis loop between the pressure 0.4~0.9 that compares, and illustrate the phosphorus doping micropore prepared in this patent/mesoporous
Carbon material has apparent meso-hole structure.In addition, phosphorus doping micropore/meso-porous carbon material relative pressure be less than 0.1 before to nitrogen
Gas has apparent absorption, illustrates the presence of microcellular structure.
The mesoporous pore size distribution curve of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1 is shown in Fig. 3.It can be seen that phosphorus
Doped micropore/meso-porous carbon material gives a strong peak value at 3.58nm, further proves phosphorus doping micropore/Jie prepared
Hole carbon material has meso-hole structure.
The micropore size distribution curve of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1 is shown in Fig. 4.It can be seen that phosphorus
Doped micropore/meso-porous carbon material gives a strong peak value at 0.79nm, further proves phosphorus doping micropore/Jie prepared
Hole carbon material has microcellular structure.
The P2p x-ray photoelectron spectroscopy curves of phosphorus doping micropore/meso-porous carbon material prepared by embodiment 1 are shown in Fig. 5.It can be with
Find out, phosphorus doping micropore/meso-porous carbon material gives two strong spectral peaks at 132.9eV and 134.6eV, it was demonstrated that the phosphorus of preparation
It is doped with phosphorus atoms in doped micropore/meso-porous carbon material.
Embodiment 2
(1) 20g gumbos are cleaned up with clear water, is dried 24 hours under the conditions of 100 DEG C, it is former to obtain dry gumbo
Material, product quality is 18g.
(2) the drying gumbo for obtaining step (1) is as (Beijing Fourth Ring freeze drier, LGJ-30H) in freeze dryer ,-
It is lyophilized 48 hours under the conditions of 45 DEG C, obtains freeze-drying gumbo, product quality is 16g.
(3) the freeze-drying gumbo for obtaining step (2) is heat-treated 2 hours at 700 DEG C, obtains phosphorus doping micropore/mesoporous carbon materials
Material, product quality is 12g.
Prepared phosphorus doping micropore/meso-porous carbon material is three-dimensional porous structure, and micropore pore size is 0.8nm, micropore hole
Volume is 0.4cm3/ g, mesoporous pore size are 6nm, pore volume 1.0cm3/ g, BET specific surface area 700m2/g；Phosphorus atoms
Doping content is 10wt%.
Embodiment 3
(1) 30g gumbos are cleaned up with clear water, is dried 36 hours under the conditions of 110 DEG C, it is former to obtain dry gumbo
Material, product quality is 27g.
(2) the drying gumbo for obtaining step (1) is as (Beijing Fourth Ring freeze drier, LGJ-30H) in freeze dryer ,-
It is lyophilized 96 hours under the conditions of 60 DEG C, obtains freeze-drying gumbo, product quality is 24g.
(3) the freeze-drying gumbo for obtaining step (2) is heat-treated 4 hours at 800 DEG C, obtains phosphorus doping micropore/mesoporous carbon materials
Material, product quality is 18g.
Prepared phosphorus doping micropore/meso-porous carbon material is three-dimensional porous structure, and micropore pore size is 1.0nm, micropore hole
Volume is 0.5cm3/ g, mesoporous pore size are 7nm, pore volume 1.1cm3/ g, BET specific surface area 750m2/g；Phosphorus atoms
Doping content is 8wt%.
Embodiment 4
(1) 40g gumbos are cleaned up with clear water, is dried 24 hours under the conditions of 110 DEG C, it is former to obtain dry gumbo
Material, product quality is 36g.
(2) the drying gumbo for obtaining step (1) is as (Beijing Fourth Ring freeze drier, LGJ-30H) in freeze dryer ,-
It is lyophilized 48 hours under the conditions of 60 DEG C, obtains freeze-drying gumbo, product quality is 32g.
(3) the freeze-drying gumbo for obtaining step (2) is heat-treated 2 hours at 800 DEG C, obtains phosphorus doping micropore/mesoporous carbon materials
Material, product quality is 24g.
Prepared phosphorus doping micropore/meso-porous carbon material is three-dimensional porous structure, and micropore pore size is 1.2nm, micropore hole
Volume is 0.6cm3/ g, mesoporous pore size are 8nm, pore volume 1.2cm3/ g, BET specific surface area 800m2/g；Phosphorus atoms
Doping content is 6wt%.
Embodiment 5
(1) 50g gumbos are cleaned up with clear water, is dried 36 hours under the conditions of 120 DEG C, it is former to obtain dry gumbo
Material, product quality is 45g.
(2) the drying gumbo for obtaining step (1) is as (Beijing Fourth Ring freeze drier, LGJ-30H) in freeze dryer ,-
It is lyophilized 96 hours under the conditions of 80 DEG C, obtains freeze-drying gumbo, product quality is 40g.
(3) the freeze-drying gumbo for obtaining step (2) is heat-treated 4 hours at 900 DEG C, obtains phosphorus doping micropore/mesoporous carbon materials
Material, product quality is 30g.
Prepared phosphorus doping micropore/meso-porous carbon material is three-dimensional porous structure, and micropore pore size is 1.5nm, micropore hole
Volume is 0.78cm3/ g, mesoporous pore size are 9nm, pore volume 1.3cm3/ g, BET specific surface area 850m2/g；Phosphorus atoms
Doping content is 5wt%.
Embodiment 6
(1) 60g gumbos are cleaned up with clear water, is dried 24 hours under the conditions of 120 DEG C, it is former to obtain dry gumbo
Material, product quality is 54g.
(2) the drying gumbo for obtaining step (1) is as (Beijing Fourth Ring freeze drier, LGJ-30H) in freeze dryer ,-
It is lyophilized 48 hours under the conditions of 80 DEG C, obtains freeze-drying gumbo, product quality is 48g.
(3) the freeze-drying gumbo for obtaining step (2) is heat-treated 2 hours at 900 DEG C, obtains phosphorus doping micropore/mesoporous carbon materials
Material, product quality is 36g.
Prepared phosphorus doping micropore/meso-porous carbon material is three-dimensional porous structure, and micropore pore size is 1.8nm, micropore hole
Volume is 0.8cm3/ g, mesoporous pore size are 10nm, pore volume 1.5cm3/ g, BET specific surface area 900m2/g；Phosphorus atoms
Doping content is 4wt%.
Claims (3)
1. a kind of preparation method of phosphorus doping micropore/meso-porous carbon material, its step are as follows：
(1) 10g~60g gumbos are cleaned up with clear water, dries 24 hours~36 hours, obtains under the conditions of 100 DEG C~120 DEG C
Obtain dry gumbo raw material；
(2) the drying gumbo for obtaining step (1) is as (Beijing Fourth Ring freeze drier, LGJ-30H) in freeze dryer, -45 DEG C
It is lyophilized 48 hours~96 hours under the conditions of~-80 DEG C, obtains freeze-drying gumbo；
(3) the freeze-drying gumbo for obtaining step (2) is heat-treated 2 hours~4 hours under the conditions of 700 DEG C~900 DEG C, obtains phosphorus and mixes
Miscellaneous micropore/meso-porous carbon material.
2. a kind of phosphorus doping micropore/meso-porous carbon material, it is characterised in that：It is to be prepared by claim 1 the method.
3. a kind of phosphorus doping micropore/meso-porous carbon material as claimed in claim 2, it is characterised in that：Prepared phosphorus doping is micro-
Hole/meso-porous carbon material is three-dimensional porous structure, and micropore pore size is 0.5~1.8nm, and micropore pore volume is 0.3~0.8cm3/ g,
Mesoporous pore size is 5~10nm, and pore volume is 0.8~1.5cm3/ g, BET specific surface area are 600~900m2/ g, phosphorus atoms are mixed
Miscellaneous content is 4~12wt%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170009171A1 (en) * | 2015-07-07 | 2017-01-12 | Nanotech Industrial Solutions, Inc. | Industrial lubricant including metal chalcogenide particles and phosphorus-based additive |
| CN106672938A (en) * | 2017-03-22 | 2017-05-17 | 兰州理工大学 | Phosphor-doped mesoporous carbon material and microwave preparation method thereof |
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- 2018-06-11 CN CN201810591723.1A patent/CN108609604A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170009171A1 (en) * | 2015-07-07 | 2017-01-12 | Nanotech Industrial Solutions, Inc. | Industrial lubricant including metal chalcogenide particles and phosphorus-based additive |
| CN106672938A (en) * | 2017-03-22 | 2017-05-17 | 兰州理工大学 | Phosphor-doped mesoporous carbon material and microwave preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZHONGWEI TIAN ET AL.: "The direct carbonization of algae biomass to hierarchical porous carbons and CO2 adsorption properties", 《MATERIALS LETTERS》 * |
| 唐羽等: "豆腐为原料的多孔炭的制备及其储锂性能研究", 《炭素技术》 * |
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Application publication date: 20181002 |