CN106744937A - The preparation method and purposes of a kind of graphitization grading-hole Carbon Materials of N doping - Google Patents
The preparation method and purposes of a kind of graphitization grading-hole Carbon Materials of N doping Download PDFInfo
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Abstract
The present invention relates to the preparation method and purposes of a kind of graphitization grading-hole Carbon Materials of N doping, the method is using biomass as raw material, mix with nitrogen source and catalyst, the graphitization grading-hole Carbon Materials of the big N doping of specific surface area are obtained after being reacted through high-temperature activation atmosphere.The graphitization grading-hole Carbon Materials of the N doping obtained by the method for the invention, nitrogen content is 3 10 %, and degree of graphitization is 5 30 %, and various test results show：The material is micropore, mesoporous and macropore activated carbon composite, and its specific surface area is about 1,500 2000 m2g‑1, between 12,25,5 10,15 50,50 100 nanometers, pore volume is 0.8 1.2 cm to its pore-size distribution3g‑1, average pore size is 10 15 nm.Pore structure with good electric conductivity and prosperity, adsorption capacity is more than 15mg/g, and salt rejection rate is up to 90%.The method of the invention raw material resources are enriched, simple and easy to get, are easy to operation, and energy consumption is relatively low, is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of the graphitization grading-hole Carbon Materials of N doping, and such Carbon Materials conduct
The application of capacitive desalination.
Background technology
Capacitive desalination (Capacitive Deionization, CDI) due to low energy consumption, easy to operate, high efficiency, it is pollution-free,
Inexpensive and renewable the advantages of, is widely used in haline water desalination.In recent years, the graphitization grading-hole Carbon Materials of N doping by
In its good electric conductivity, flourishing pore structure be considered as a kind of efficient capacitive desalination electrode material.Wherein, N doping
With the electric conductivity that graphitization can greatly improve charcoal, good electric conductivity be conducive to improve capacitive desalination adsorption desorption speed；
Hierarchical porous structure (integrating micropore, mesoporous and macropore) can make it while having adsorption capacity and adsorption desorption speed high.
But the graphitization grading-hole Carbon Materials of N doping are prepared by traditional additional nitrogen source of various templates more, and the method building-up process is answered
Miscellaneous, template and presoma high cost, nitrogen content and degree of graphitization are whard to control, and grading-hole is difficult to, it is difficult to realize magnanimity
Change and prepare, limit its practical application.Recently, researchers propose, using the method for self form, to prepare the graphitization of N doping
Grading-hole charcoal.Wherein, it is one of method for having wide application prospects to prepare this kind of charcoal using biomass self form, because raw
Material has natural foraminous die plate structure, nitrogen content high, abundance, with low cost.
Cotton stalk, vegetable seed slag, fruit tree, walnut shell, the bar denier wood biomass such as shell, as agricultural wastes, are Xinjiang, complete
Even all over the world compared with the biomass resource of horn of plenty, carbon content accounts for 40-60% for state, is the graphitization classification for preparing N doping
The high-quality presoma of hole charcoal, additionally, these biomass have natural vascular bundle macroporous structure, quality is hard, thickness of pipe wall, its charcoal
Skeleton stabilization, rich in inorganic elements such as iron, silicon, aluminium, phosphorus and potassium, on the one hand these elements are the oxidation of nanostructured after charing
Thing, can as mesoporous or micropore template, on the other hand can as the graphitization of catalyst charcoal, it follows that these
Biomass are to prepare the ideal presoma of classification mesoporous activated carbon.Therefore, the present invention intends with Xinjiang cotton stalk, vegetable seed slag, fruit tree
The biomass such as branch, walnut shell, Badamu shell are presoma, and activation and catalytic activation are combined by catalyzing and carbonizing, physical chemistry
Method regulate and control its pore-size distribution, improve its specific surface area, preparation integrate micropore, mesoporous and macropore capacitive desalination height
The graphitization grading-hole charcoal of specific surface area N doping, and use it for capacitive desalination.
The content of the invention
It is an object of the present invention to be directed to the defect of existing capacitive desalination charcoal, there is provided a kind of graphitization classification of N doping
The preparation method and purposes of hole Carbon Materials, the method mix, through high-temperature activation using biomass as raw material with nitrogen source and catalyst
The graphitization grading-hole Carbon Materials of the big N doping of specific surface area are obtained after atmosphere reaction.Compared with prior art, institute of the present invention
It is raw material that the method for stating uses biomass, because biomass have abundant loose structure, therefore is provided to prepare grading-hole charcoal
Ensure.The results showed：The graphitization grading-hole Carbon Materials of the N doping obtained by the method for the invention, nitrogen content is
3-10%, degree of graphitization is 5-30%, and various test results show：The material is micropore, mesoporous and macropore activated carbon composite, its ratio
Surface area is about 1500-2000m2g-1, its pore-size distribution between 1-2,2-5,5-10,15-50,50-100 nanometer, pore volume
It is 0.8-1.2cm3g-1, average pore size is 10-15nm.Pore structure with good electric conductivity and prosperity, adsorption capacity is big
In 15mg/g, salt rejection rate is up to 90%.The method of the invention raw material resources enrich, it is simple and easy to get, be easy to operation, energy consumption compared with
It is low, it is suitable for large-scale industrial production.The method of the invention raw material resources enrich, it is simple and easy to get, be easy to operation, energy consumption compared with
It is low, it is suitable for large-scale industrial production.
A kind of preparation method of the graphitization grading-hole Carbon Materials of N doping of the present invention, the method is with biomass
Raw material, using activator, prepares the graphitization grading-hole charcoal of N doping, and concrete operations follow these steps to carry out：
A, by biomass cotton stalk, vegetable seed slag, fruit tree, walnut shell or bar denier wood shell be raw material, with nitrogen source be urea, sulphur
Urea, lysine or cysteine, graphitization catalyst are nickelous carbonate, iron oxide, ferric carbonate, molybdenum oxide, carbonic acid molybdenum salt, oxidation
Brill, salt cobalt carbonate and tungsten oxide or carbonic acid tungsten uniformly mix, and obtain biomass and nitrogen source and the mixture of graphitization catalyst, its
Middle biomass material is 1 with the mass ratio of nitrogen source:0.1-1；Biomass material is 1 with the mass ratio of catalyst:0.01-0.5；
B, the mixture for obtaining step a are in flow for the activator containing gas of 10-300cc/min is nitrogen, ammonia, sulphur
Change under hydrogen or the protection of hydrogen-argon-mixed activation phenomenon, 400-1000 DEG C of temperature is reacted 0.5-3 hours, is then cooled down, in acidity
It is 5-7 to be washed in solution phosphoric acid, hydrochloric acid or nitric acid to pH value, is drying to obtain the graphitization grading-hole Carbon Materials of N doping.
Nitrogen source described in step a is urea or thiocarbamide.
Gas activation agent described in step b is nitrogen or ammonia.
Reaction temperature described in step b is 900 DEG C.
Acid solution described in step b is phosphoric acid or hydrochloric acid.
Purposes of the graphitization grading-hole Carbon Materials of the N doping that methods described is obtained in capacitive desalination is prepared.
Capacitive desalination includes desalination electrode, desalination electrolytic cell and treats desalting soln.
The preparation method of the graphitization grading-hole Carbon Materials of N doping of the present invention, is surveyed by using nitrogen adsorption desorption
Examination, the graphitization grading-hole Carbon Materials of the N doping for being obtained have large specific surface area, and its surface area is up to 1500-
2000m2/ g, between 1-2,2-5,5-10,15-50,50-100 nanometer, pore volume is about 0.8-1.2cm to its pore-size distribution3g-1, average pore size is 10-15nm.
The preparation method of the graphitization grading-hole Carbon Materials of N doping of the present invention, by using XRD and Raman light
Spectrum test, the graphitization grading-hole Carbon Materials of the N doping for being obtained have significant graphite peaks.
The preparation method of the graphitization grading-hole Carbon Materials of N doping of the present invention, by using elementary analysis and
XPS is tested, and the graphitization grading-hole Carbon Materials of the N doping for being obtained have nitrogen content higher, and nitrogen content is 5%.
The graphitization grading-hole Carbon Materials for obtaining N doping of the present invention are used as capacitive desalination electrode material, desalting ability
By force, and cost is relatively low, aboundresources, it is nontoxic.
Present invention also offers a kind of capacitive desalination device, the device is by (1) electrochemical workstation；(2) first nitrogen are mixed
Miscellaneous graphitization classification pore carbon electrode；The graphitization classification pore carbon electrode of (3) second N dopings；(4) haline water；(5) delivery port；
(6) water inlet；(7) fresh water；(8) electric conductivity measuring instrument composition, it is consolidated by the graphitization grading-hole charcoal of N doping of the present invention
Surely stainless steel electrode surface is arrived to be obtained.
Capacitive desalination is a kind of new high salt water desalination apparatus, with low energy consumption, easy to operate, high efficiency, it is pollution-free, low into
This and it is renewable the advantages of, therefore, be widely used in haline water desalination.The present invention proves of the present invention by charge-discharge test
The graphitization grading-hole Carbon Materials of the N doping that preparation method is obtained have preferable capacitive desalination performance, and result of study shows：
Constant current charge-discharge potential region of the N doping graphitization grading-hole Carbon Materials under 0.1-10 amperes every gram of current density is 0
Between~1.2V, electrochemical desalting capacity is dramatically increased, with larger ion storage ability, and in electric double layer capacitance and counterfeit electricity
Hold two aspects and show excellent performance and application value.
Present invention also offers a kind of capacitive desalination device, by N doping of the present invention graphitization classification Porous materials with
Electroconductive binder, conductive black premix are coated on 5 × 5cm2Stainless (steel) wire current collector on, extruding film forming be obtained, wherein described
The graphitization grading-hole Carbon Materials and electroconductive binder of N doping, the ratio of conductive black are 1:0.1-0.2:0.1-0.2.It is preferred that
, the graphitization grading-hole Carbon Materials and electroconductive binder of the N doping, the ratio of conductive black are 1:0.15:0.05.
Brief description of the drawings
Fig. 1 is the graphitization grading-hole Carbon Materials high resolution scanning and transmission electron microscope picture of N doping in the embodiment of the present invention 1,
Wherein (a) scanning electron microscope (SEM) photograph；(b) transmission electron microscope picture；
Fig. 2 is the nitrogen adsorption desorption curve map of the graphitization grading-hole Carbon Materials of N doping in the embodiment of the present invention 1, wherein
A () is nitrogen adsorption curve；B () is pore size distribution curve；
Fig. 3 is the infrared and elementary analysis XPS figures of the graphitization grading-hole Carbon Materials of N doping in the embodiment of the present invention 1,
Wherein (a) is infrared spectrum；B () is x-ray photoelectron spectroscopy；
Fig. 4 is the graphitization grading-hole Carbon Materials capacitive desalination device of N doping in the embodiment of the present invention 1, wherein (1) is electric
Chem workstation；The graphitization classification pore carbon electrode of (2) first N dopings；The graphitization grading-hole charcoal electricity of (3) second N dopings
Pole；(4) electrolyte；(5) delivery port；(6) water inlet；(7) fresh water；(8) electric conductivity measuring instrument；
Fig. 5 is current density of the graphitization grading-hole Carbon Materials of N doping in the embodiment of the present invention 1 at 0.2 ampere every gram
Under constant current charge-discharge figure.
Specific embodiment
For a further understanding of the present invention, with reference to embodiment, the present invention is described in detail.
Embodiment 1：
A, to weigh 2g biomass vegetable seed ground-slag end and nitrogen source be that urea and catalyst are nickelous carbonate with mass ratio 1:0.5:0.5 mixes
Close uniform, obtain mixture；
B, the mixture that step a is obtained is transferred in high temperature furnace, in flow for the activator containing gas of 10cc/min is hydrogen
Under argon-mixed activation phenomenon protection, 900 DEG C of temperature is reacted 1 hour, is then cooled down, and is washed to pH with 2M dilute phosphoric acid solutions
It is 6-7 to be worth, and is drying to obtain the graphitization grading-hole Carbon Materials of N doping.
Using SEM, transmission electron microscope, infrared, elemental analyser etc. to the graphite of gained N doping
The characterization result that change grading-hole Carbon Materials carry out physicochemical property is shown in Fig. 1, Fig. 2 and Fig. 3, to the graphitization point of obtained N doping
Level hole Carbon Materials carry out capacitive desalination test, as a result see Fig. 4 and Fig. 5.
Fig. 1, Fig. 2 and Fig. 3 result show that the graphitization grading-hole Carbon Materials specific surface area of gained N doping is
1990.23m2g-1, between 1-2,2-5,5-10,15-50,50-100 nanometer, pore volume is about 0.8-1.2cm to pore-size distribution3g-1, average pore size is 10-15nm.Elementary analysis mass percent is carbon 82.63%, oxygen 10.19%, nitrogen 5.52%.Fig. 4 and Fig. 5
Result shows that its desalting performance is good, and its desalination capacity is 362F g-1。
Embodiment 2
A, by 2g biomass cotton stalks powder be raw material, with nitrogen source be thiocarbamide, graphitization catalyst be iron oxide in mass ratio
1:0.1:0.01 is well mixed, and obtains mixture；
B, the mixture that step a is obtained is transferred in high temperature furnace, in flow for the activator containing gas of 50cc/min is sulphur
Change under the activation phenomenon protection of hydrogen, 800 DEG C of temperature is reacted 2 hours, is then cooled down, and is washed to pH value with 2M dilute hydrochloric acid solutions and is
5-7, is drying to obtain the graphitization grading-hole Carbon Materials of N doping.
The analysis of nitrogen adsorption desorption, the graphitization grading-hole Carbon Materials specific surface area of elemental analyser detection gained N doping are
1820m2g-1, aperture is between 2-5,5-10,15-50,50-100 nanometer；Elementary analysis mass percent is carbon 78.1%, oxygen
13%, nitrogen 3%.Desalination capacity is 320F g-1。
Embodiment 3
A, by 2g biomass bars denier wood shell be raw material, with nitrogen source be urea, graphitization catalyst be iron oxide in mass ratio 1:
0.2:0.05 is well mixed, and obtains mixture；
B, the mixture that step a is obtained is transferred in high temperature furnace, in flow for the activator containing gas of 100cc/min is nitrogen
Under the activation phenomenon protection of gas, 900 DEG C of temperature is reacted 0.5 hour, is then cooled down, and is washed to pH value with 2M dilute nitric acid solutions and is
5-7, is drying to obtain the graphitization grading-hole Carbon Materials of N doping.
The analysis of nitrogen adsorption desorption, the graphitization grading-hole Carbon Materials specific surface area of elemental analyser detection gained N doping are
1500m2g-1, aperture is between 2-5,5-10,15-50,50-100 nanometer；Elementary analysis mass percent is carbon 85.30%, oxygen
4.71%, nitrogen 4.82%.Desalination capacity is 280F g-1。
Embodiment 4
A, by 2g biomass apple trees branch be raw material, with nitrogen source be lysine, graphitization catalyst be ferric carbonate press matter
Amount compares 1:1:0.5 is well mixed, the mixture for obtaining；
B, the mixture that step a is obtained is transferred in high temperature furnace, in flow for the activator containing gas of 200cc/min is hydrogen
Under argon-mixed activation phenomenon protection, 400 DEG C of temperature is reacted 1 hour, is then cooled down, and is washed to pH with 2M dilute phosphoric acid solutions
It is 5-7 to be worth, and is drying to obtain the graphitization grading-hole Carbon Materials of N doping.
The analysis of nitrogen adsorption desorption, the graphitization grading-hole Carbon Materials specific surface area of elemental analyser detection gained N doping are
1674m2g-1, aperture is between 2-5,5-10,15-50,50-100 nanometer；Elementary analysis mass percent is carbon 92.11%, oxygen
4.52%, nitrogen 3.31%.Desalination capacity is 290F g-1。
Embodiment 5
A, by 2g biomass jujube trees branch be raw material, with nitrogen source be cysteine, graphitization catalyst be molybdenum oxide press matter
Amount compares 1:0.4:0.1 uniform mixing, obtains mixture；
B, the mixture that step a is obtained is transferred in high temperature furnace, in flow for the activator containing gas of 300cc/min is nitrogen
Under the activation phenomenon protection of gas, 600 DEG C of temperature is reacted 3 hours, is then cooled down, and it is 5- to be washed to pH value with 2M dilute hydrochloric acid solutions
7, it is drying to obtain the graphitization grading-hole Carbon Materials of N doping.
The analysis of nitrogen adsorption desorption, the graphitization grading-hole Carbon Materials specific surface area of elemental analyser detection gained N doping are
1840m2g-1, hole characteristic is mesoporous micropore macropore mix aperture；Elementary analysis mass percent result is carbon 82.43%, oxygen
8.02%, nitrogen 5.61%.Desalination capacity is 279F g-1。
Embodiment 6
A, by 2g biomass walnut shell be raw material, with nitrogen source be urea, graphitization catalyst be cobalt oxide press 1:0.5:0.5 mixes
Close uniform, obtain biomass with nitrogen source and the mixture of graphitization catalyst, wherein biomass material is with the mass ratio of nitrogen source
10.1-1；Biomass material is 10.01-0.5 with the mass ratio of catalyst；
B, the mixture for obtaining step a are in flow for the activator containing gas of 300cc/min is the activation phenomenon of ammonia
Under protection, 1000 DEG C of temperature is reacted 0.5 hour, is then cooled down, and it is 5-7 to be washed to pH value with 2M dilute hydrochloric acid solutions, is drying to obtain
The graphitization grading-hole Carbon Materials of N doping.
The analysis of nitrogen adsorption desorption, the graphitization grading-hole Carbon Materials specific surface area of elemental analyser detection gained N doping are
1542m2g-1, hole characteristic is mesoporous micropore macropore mix aperture；Elementary analysis mass percent result is carbon 81.41%, oxygen
9.22%, nitrogen 4.46%, desalination capacity is 279F g-1。
Embodiment 7
Cyclic voltammetry
Prepare capacitive desalination device：The device is by the graphitization grading-hole charcoal electricity of electrochemical workstation 1, the first N doping
After pole 2, graphitization classification pore carbon electrode 3, high salt concentration electrolyte 4, delivery port 5, the water inlet 6, desalination of the second N doping
Fresh water 7 and electric conductivity measuring instrument 8 are constituted；The graphitization grading-hole Carbon Materials of the N doping of 60mg and 30mg electroconductive binders are mixed
It is even to be coated in the online compressing tablet film forming of stainless steel battery current collecting, it is respectively prepared the graphitization classification He of pore carbon electrode 2 of the first N doping
The graphitization classification pore carbon electrode 3 of the second N doping, and insert to make flowing/static electrolytic cell by oneself as working electrode
In, the graphitization classification pore carbon electrode 3 of the graphitization of the first N doping classification N doping of pore carbon electrode 2 and second respectively with electrification
One end connection of work station 1 is learned, the sodium chloride electrolyte of 25mL 200mg/L is added in the reactor, in the bottom of reactor point
Delivery port 5 and water inlet 6 are not provided with, and the liquid after being electrolysed in reacted device enters de- after electric conductivity measuring instrument 8 is determined
In fresh water 7 after salt, using CHI660E electrochemical workstations 1 in different voltage ranges, respectively in 5mVs-1-500mVs-1's
Sweep and sweep cyclic voltammetry curve under speed, the different specific capacitances for sweeping single electrode under speed are calculated and obtained with these cyclic voltammetry curves.
Embodiment 8
Prepare capacitive desalination device：Carried out by embodiment 7：
The graphitization grading-hole Carbon Materials of the N doping of 60mg and 30mg electroconductive binders are mixed and is coated in stainless steel electricity
Compressing tablet film forming on the currect collecting net of pond, the graphitization for being respectively prepared the first N doping is classified the graphite of the N doping of pore carbon electrode 2 and second
Change classification pore carbon electrode 3, and be positive and negative two electrode, the sodium chloride of 25mL 200mg/L is measured for electrolyte, to make stream by oneself
Dynamic/static electrolytic cell is reactor, using blue electricity battery test system in different voltage ranges, applies different electric currents close
Degree, carries out charge-discharge test, respectively in 0.1-10Ag-1Current density under discharge and recharge, to obtain desalination capacity.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improvement and modification are also fallen into the present invention.
Claims (6)
1. the preparation method of the graphitization grading-hole Carbon Materials of a kind of N doping, it is characterised in that with biomass as raw material, uses
Activator, prepares the graphitization grading-hole charcoal of N doping, and concrete operations follow these steps to carry out：
A, by biomass cotton stalk, vegetable seed slag, fruit tree, walnut shell or bar denier wood shell be raw material, with nitrogen source be urea, thiocarbamide, rely
Propylhomoserin or cysteine, graphitization catalyst are nickelous carbonate, iron oxide, ferric carbonate, molybdenum oxide, carbonic acid molybdenum salt, oxidation brill, salt carbon
Sour cobalt and tungsten oxide or carbonic acid tungsten uniformly mix, and biomass and nitrogen source and the mixture of graphitization catalyst are obtained, wherein biological
Matter raw material is 1 with the mass ratio of nitrogen source:0.1-1；Biomass material is 1 with the mass ratio of catalyst:0.01-0.5；
B, the mixture for obtaining step a are in flow for the activator containing gas of 10-300 cc/min is nitrogen, ammonia, vulcanization
Under hydrogen or the protection of hydrogen-argon-mixed activation phenomenon, 400-1000 DEG C of temperature is reacted 0.5-3 hours, is then cooled down, molten in acidity
It is 5-7 to be washed in liquid phosphoric acid, hydrochloric acid or nitric acid to pH value, is drying to obtain the graphitization grading-hole Carbon Materials of N doping.
2. the preparation method of the graphitization grading-hole Carbon Materials of N doping according to claim 1, it is characterised in that step a
The nitrogen source is urea or thiocarbamide.
3. the preparation method of the graphitization grading-hole Carbon Materials of N doping according to claim 1, it is characterised in that step b
Described in gas activation agent be nitrogen or ammonia.
4. the preparation method of the graphitization grading-hole Carbon Materials of N doping according to claim 1, it is characterised in that step b
Described in reaction temperature be 900 DEG C.
5. the preparation method of the graphitization grading-hole Carbon Materials of N doping according to claim 1, it is characterised in that step b
Described in acid solution be phosphoric acid or hydrochloric acid.
6. according to claim 1 method obtain N doping graphitization grading-hole Carbon Materials in capacitive desalination is prepared
Purposes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109321211A (en) * | 2018-10-19 | 2019-02-12 | 福州大学 | A kind of graphitization graded porous carbon composite phase-change energy storage material and preparation method thereof |
| CN110436459A (en) * | 2019-09-19 | 2019-11-12 | 盐城工学院 | A kind of preparation method being graphitized graded porous carbon |
| CN110841595A (en) * | 2019-12-02 | 2020-02-28 | 国网江苏省电力有限公司电力科学研究院 | Preparation method and application of nitrogen-doped graphitized carbon material |
| CN113413870A (en) * | 2021-05-17 | 2021-09-21 | 中国科学院青海盐湖研究所 | Magnesium oxide-metal sulfide-biomass charcoal composite material and preparation method and application thereof |
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| CN113413870A (en) * | 2021-05-17 | 2021-09-21 | 中国科学院青海盐湖研究所 | Magnesium oxide-metal sulfide-biomass charcoal composite material and preparation method and application thereof |
| CN113413870B (en) * | 2021-05-17 | 2022-11-25 | 中国科学院青海盐湖研究所 | Magnesium oxide-metal sulfide-biomass charcoal composite material and preparation method and application thereof |
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